Biosci. Biotechnol. Biochem.

, 73 (5), 971979, 2009

Award Review

Synthetic Studies of Natural 10-Membered Lactones, Mueggelone, Microcarpalide, and Sch 642305, Which Have Interesting Bioactivities
Ken I SHIGAMI
Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Online Publication, May 7, 2009 [doi:10.1271/bbb.80877]

A number of 10-membered lactones have been isolated as secondary metabolites, and many of them have interesting and potent activities. Because of synthetic and biological interests, many synthetic studies of these compounds have been made. This review summarizes synthetic approaches to three natural 10membered lactones, mueggelone, microcarpalide, and Sch 642305. Mueggelone is an inhibitor of sh development, microcarpalide is a microlament disrupting agent, and Sch 642305 is an inhibitor of bacterial DNA primase. Key words: 10-membered lactone; mueggelone; microcarpalide; Sch 642305; total synthesis

isolated from a bloom-foaming strain of Aphanizomenon os-aquae in 1997.5) With mueggelone at a concentration of 10 mg/ml, zebra sh larvae showed 45% mortality, and the surviving larvae showed edema in the heart region and thrombosis. This compound is thought to play an ecologically important role in inhibition of the development of herbivorous sh. Mueggelone was found to have a 10-membered lactone and trans-epoxide by spectroscopic analysis; however, no information has been reported on the absolute conguration of the three stereocenters. This compound was re-isolated from bluegreen alga, Gloeotrichia sp., in 1998 by another group,6) but stereochemistry was not mentioned. 1. Our rst synthesis of mueggelone The rst synthesis of mueggelone was accomplished by our group in 2000 (Scheme 1 [1]).7,8) We undertook the synthesis of all four possible stereoisomers of mueggelone, which have trans epoxide, to determine the absolute conguration. In order to prepare the four stereoisomers eciently, we selected the key intermediate 4, which can be transformed into any of the four stereoisomers via asymmetric reduction of a ketone, macrolactonization, and nally epoxide formation. The side chain part was synthesized from alcohol 1, which was obtained from D-arabinose according to the established procedure.9) Alcohol 1 was converted to aldehyde 2 via construction of Z-olen by Wittig reaction. The best ratio (E/Z = 1:10) in this Wittig reaction was provided using NaHMDS as a base, and these isomers were easily separated by AgNO3 -impregnated silica gel column chromatography. Aldehyde 2 was subjected to the HornerWadsworthEmmons reaction to give the key intermediate 4. Under a condition using n-BuLi as a base, the E/Z ratio was 96:4; however, partial epimerization (25%) of the TBSO group was observed. On the other hand, the procedure employing DBULiCl10) resulted in very little epimerization (12%) with excellent E/Z selectivity (E/Z = >99:1). Now that the key intermediate was obtained enantioselectively, we tried several conditions for asymmetric reduction of the enone 4, and the best selectivity (/ = 9:1 or 1:9) was obtained with the (S)- or (R)-CBS-reagent11,12) and boraneTHF complex. After conrmation of the stereochemistry of each isomer by the modied Moshers

Many 10-membered lactones have been isolated as secondary metabolites of terrestrial and marine organisms, such as bacteria, fungi, and plants. Synthetic studies on these compounds are meaningful, as well as biological studies, because their bioactivities are frequently concerned with structure. The rst naturally occurring 10-membered lactone is jasmine ketolactone, which was isolated in 19421) as a component of essential oil of Jasminum grandiorium, and whose structure was conrmed in 1964.2) Diplodialide A is the rst bioactive 10-membered lactone isolated from a fungus as a steroid hydroxylase inhibitor, in 1975.3) After that, this class of compounds attracted many organic chemists, and many synthetic studies have been reported. In synthesizing these compounds, the key reaction is the construction of a 10-membered ring. Lactonization was most common as a ring-closing step before the development of ringclosing metathesis (RCM).4) Recently, construction of the lactone ring by RCM has been increasing remarkably. This review centers on synthetic approaches to three 10-membered lactones, mueggelone, microcarpalide, and Sch 642305. All of three lactones were found as microbial secondary metabolites, and synthetic approaches have been reported by many groups, including us, motivated by their potent activities.

I. Synthetic Approaches to Mueggelone

Mueggelone has attracted the keen interest of scientists for its unique activity and structure since it was

This review was written in response to the authors receipt of The Japan Bioscience, Biotechnology, and Agrochemistry Society Award for the Encouragement of Young Scientists in 2008. Correspondence: Tel: +81-3-5841-5120; Fax: +81-3-5841-8019; E-mail: aishig@mail.ecc.u-tokyo.ac.jp

972
O O O O Diplodialide A Jasmine ketolactone OH OH Hexn O O OH Microcarpalide (B) Mueggelone (A) O HO O O O O O O

K. ISHIGAMI

O Sch 642305 (C)

Fig. 1. Natural 10-Membered Lactones.

method,13) hydrolysis was followed by Yamaguchi lactonization14) to give 10-membered lactone 5 and 6 in satisfactory yield, together with a small amount of a dimeric lactone (510%). On the other hand, the Corey Mukaiyama method15) was found to give only several unidentiable compounds. In the following epoxide formation stage, we succeeded in controlling the stereochemistry of the epoxide by the direction of elimination, that is, mueggelone and (9R,12R,13R)-isomer were obtained from 5 by changing the position of the leaving group. In the same way, (9S,12S,13S)- and (9S,12R,13R)-isomer were synthesized from 6. With the four stereoisomers in hand, we analyzed the NMR spectra and specic rotations carefully. It was hard to distinguish these isomers by 1 H NMR, but in the 13 C NMR spectra an obvious dierence was observed. In addition, the sign of specic rotation (natural: +28.3, synthetic: +28.7) showed that natural mueggelone had an absolute conguration of 9R,12S,13S. Thus we succeeded in the ecient synthesis of four stereoisomers and in the determination of the stereochemistry of mueggelone.

2. Synthesis of mueggelone by Yadav et al. Yadav et al. reported the synthesis of mueggelone in 2008 (Scheme 1 [2]),16) introducing all three stereocenters by Sharpless asymmetric epoxidation (AE).17) Their key reaction was olen cross metathesis between side chain moiety 10 and lactone moiety 15 in the nal step of synthesis. The side chain moiety was synthesized from skipped diyne 7, which was prepared from propargyl alcohol. Diyne 7 was partially reduced to allylic alcohol 8, and was subjected to Sharpless AE17) and Lindlar hydrogenation to aord epoxide 9. C1 homologation gave terminal olen 10. On the other hand, lactone moiety 15 was synthesized from allylic alcohol 11, which was prepared from 1,9-nonanediol in several steps. After Sharpless AE,17) it was converted the corresponding epoxy iodide 12. Terminal olen was introduced by a reductive epoxide opening in the presence of zinc18) to aord 13, which was converted to the corresponding hydroxy acid 14. Yamaguchi lactonization14) of hydroxy acid 14 gave lactone 15. Olen cross metathesis4,19) between precursors 10 and 15 in the presence of the 2nd-generation Grubbs catalyst20) gave mueggelone with complete E selectivity, but the yield was not very high (40%) because undesired homodimer was generated.

II. Synthetic Approaches to Microcarpalide

Microcarpalide is a 10-membered lactone, isolated from the fermentation broth of an unidentied endophytic fungus by Hemscheidt and co-workers in 2001.21) This compound acts as a strong microlament disrupting agent and shows weak cytotoxicity to mammalian cells.21) Because of the large dierence between the eective concentration for antimicrolament activity and for cytotoxicity, it is thought that this compound

[1] Our synthesis (2000) 6.0% in 17 steps from known compound 1

O SEt EtS 1 prepared from D-arabinose O OH O 8 steps 2 O (MeO)2P 3 O CO2Me
7

PMBO CHO O OTBS PMBO O 5 steps

13S

O
12S

O
9R

Mueggelone O

OTBS 3 steps CBS reduction and Yamaguchi lactonization

5 3 steps O O

(9R,12R,13R )-isomer Similarly (9S,12S,13S )- and (9S,12R,13R )-isomers

PMBO

MeO2C O

PMBO

OTBS

OTBS

[2] Yadav et al. (2008) 3.8% in 14 steps from 1,9-nonanediol

Sharpless AE and Lindlar reduction OH 7 prepared from propargyl alcohol Sharpless AE HO
7

OH 8

O OH 9 2 steps 10 O

O cross metathesis

2 steps

O
7

OH OPMB
7

OH OPMB CO2H 5 steps 14

7

Yamaguchi lactonization

OPMB 2 steps

I 12

11 prepared from 1,9-nonanediol

13

15

Scheme 1. Synthetic Approaches to Mueggelone.

Syntheses of 10-Membered Lactones

973

will be an eective tool in studies of cell motility and metastasis, and will be a potential lead structure to selective, nontoxic antiactin agents. Since the isolation of microcarpalide, a number of syntheses have been reported in the past few years. 1. First synthesis of microcarpalide by Marco et al. The rst synthesis of microcarpalide was achieved by Marco and co-workers in 2002 (Scheme 2 [1]).22,23) Their key reaction was the RCM4) of ester 18 to form 10membered lactone, and four stereocenters were derived from commercially available chiral pools. (R)-Glycidol was converted to alcohol 16 by epoxide opening with n-pentyl cuprate and subsequent chelation-controlled allylation.24) Alcohol 16 was coupled with acid 17, which was derived from (S,S)-tartaric acid,25) to aord diene ester 18, the precursor for RCM. Treatment of 18 with 1st-generation Grubbs catalyst26) under high dilution conditions (1 mM) provided a 2:1 E/Z mixture of 10membered lactone 19. On the other hand, it is worth mentioning that the use of 2nd-generation Grubbs catalyst20) resulted in the exclusive formation of undesired (Z)-19. Their theoretical calculations showed that (Z)-19 is more stable than (E)-19, by about 2 kcal/mol. The authors supposed that the E/Z ratio was no longer kinetically controlled but rather the result of a chemical equilibrium, and that it caused a marked enhancement in the percentage of (Z)-isomer.27) After isolation of (E)-isomer from the 2:1 mixture (19), deprotection gave microcarpalide. Although there was a small problem with E/Z selectivity at the ring-closing step, they achieved short and ecient synthesis of microcarpalide. 2. Other syntheses of microcarpalide employing RCM Since Marco et al. achieved the rst synthesis of microcarpalide,22) a number of syntheses have been reported. Similarly to Marcos synthesis, most of them also featured RCM of a diene ester of type 18. In their synthetic approaches, construction of the four stereocenters and selection of protecting groups, which inuence the total eciency and E/Z selectivity of RCM, are important. (1) Synthesis by Gurjar et al. Gurjar and co-workers employed diene ester 24, protected with benzyl groups and a methoxyethoxymethyl (MEM) group, as a precursor for RCM in 2003 (Scheme 2 [2]).28,29) Olenic alcohol 21 was synthesized by Sharpless asymmetric dihydroxylation (AD)30,31) of unsaturated ester 20 and the following introduction of a C2 unit. On the other hand, acid 23 was derived from the known compound 22,32,33) which was easily obtained from D-mannose. These two fragments were subjected to esterication to give the precursor for RCM. Reaction of 24 (high dilution, 1.6 mM) in the presence of 1stgeneration Grubbs catalyst26) provided E- and Z-isomers of 25 in 10:1 ratio. Finally, removal of the MEM group using TiCl4 resulted in debenzylation to aord microcarpalide. Interestingly, compared with Marcos synthesis,22) E/Z selectivity at the ring-closing step was greatly improved by changing the protective groups. Similarly, Ghosh et al. also reported a total synthesis of microcarpalide using the same precursor 24 for RCM in 2005,34) in which all four stereocenters were derived from D-mannitol (scheme not shown).

(2) Synthesis by Davoli et al. Davoli and co-workers selected tribenzyl ether 3235,36) as a precursor for RCM in their 2nd-generation synthesis in 2005, a revision of their rst synthesis in 2004 (Scheme 2 [3]).36) In the revised synthesis, they successfully exploited Mattesons asymmetric homologation3739) to introduce contiguous stereocenters, using ()- and ()-pinanediol as chiral directors. Chiral boronate 26 obtained from ()-pinanediol was subjected to asymmetric homologation to insert the rst stereocenter to give -chloro derivative. After SN 2 substitution40) of the chloride with benzyloxide, the second asymmetric center was introduced by repeating homologation to give 2-benzyloxy-1-chloroboronate 27 stereoselectively. Treatment with allylmagnesium bromide and subsequent oxidative removal of the boronic scaold aorded homoallyl alcohol 28. Similarly, boronate 29 obtained from ()-pinanediol was transformed into acid 31 by employing Mattesons asymmetric homologation twice. Alcohol 28 and acid 31 were coupled to provide ester 32. RCM of tribenzyl ether 32 (high dilution, 0.52 mM) with 1st-generation Grubbs26) catalyst resulted in exclusive formation of E-isomer 33, but with poor conversion (43%). Finally, deprotection was performed using TiCl4 , under similar conditions as Gurjars,28) to aord microcarpalide. The total yield was not sucient in their synthesis, but employing Mattesons asymmetric homologation for construction of all stereochemistry appeared to be a steady and unique approach. In 2007, Prasad et al.41) reported synthesis of microcarpalide using the same precursor for RCM. They constructed 32 from (S,S)- and (R,R)-tartaric acid in a longer reaction scheme (not shown). Interestingly, they reported that RCM of 32 using 2nd-generation Grubbs catalyst20) provided an E/Z-mixture with poor conversion (36%). (3) Synthesis by Sharma and Cherukupalli In 2006, Sharma and Cherukupalli reported a process of synthesis in which they employed diene ester 38, protected with acetonide and benzyl group, as a precursor for RCM (Scheme 2 [4]).42) Alcohol 35 was synthesized by epoxide opening of 34, which was prepared from L-ascorbic acid. The other fragment 37, involving the residual stereocenters, was prepared by Evans aldol reaction43) using 1,4-butanediol as the starting material. Connection of two fragments 35 and 37 was carried out under the Yamaguchi conditions,14) and the resulting ester 38 was subjected to RCM using 1st-generation Grubbs catalyst.26) High dilution conditions (1.4 mM) brought a result similar to Marcos group,22,23) giving a 2:1 E/Z mixture of 10-membered lactone 39 in good yield. After purication of E-isomer, deprotection successfully aorded microcarpalide. (4) Synthesis by Banwell and Loong Three further groups also reported synthesis of this compound using RCM. Banwells group (2004, entmicrocarpalide),44) Chavans group (2005),45) and Fu rstners group (2007)46) employed precursor 18 (or ent-18), the same intermediate as in Marcos synthesis.22,23) Synthesis of ent-microcarpalide by Banwell and Loong is shown in Scheme 2 [5].44) They constructed the intermediate ent-18 by cross metathesis4,19) of ,unsaturated ester 44 using 2nd-generation Grubbs catalyst20) under ethylene, because direct methylenation

974

K. ISHIGAMI

of hemiacetal 43 (conversion to ent-18) was not successful, and RCM of ,-unsaturated ester 44 did not proceed.47) Hemiacetal 43 was synthesized from alcohol 41 and acid 42, whose stereocenters originated in Sharpless AD30,31) and (S)-malic acid respectively. In their synthesis, installation of the second double bond for RCM was problematic and lowered synthetic eciency. Chavans group45) installed all four stereocenters of 18 by Sharpless AD,30,31) while Fu rstners group46) installed them by Sharpless AE17) and AD30,31) (schemes not shown). All of three groups reported that RCM of 18 (or ent-18) resulted in E/Z selectivity similar to that of Marcos group.22,23) (5) Consideration of the synthesis of microcarpalide by RCM The majority of syntheses of microcarpalide were based on RCM, as described above. In them, it was most important to construct the desired E-olen selectively at the ring-closing step. Here, two possible factors inuencing E/Z selectivity are discussed. First, selection of ruthenium catalyst for RCM is important for E/Z selectivity. As reported by Marco,22,23) Davoli,35,36) Prasad,41) and Fu rstner,46) the use of 1st26) generation Grubbs catalyst showed moderate or high E selectivity, while the use of 2nd-generation Grubbs catalyst resulted20) in enhanced formation of Z-isomer. The similar phenomenon was observed in synthesis of other medium-sized rings27) and this must be an important characteristic of RCM. In many syntheses of medium-sized rings by RCM, formation of the E/Zmixture was observed. Generally, olens formed by RCM were sensitive to the reverse reaction, such as ring opening metathesis (ROM), because of the internal ring strain. 2nd-generation Grubbs catalyst tends to form thermodynamically stable isomers, so Z-isomers are favored in the case of a strained medium-sized ring.27) Second, the selection of protecting groups to be attached to the precursor is also important for reactivity and E/Z selectivity in RCM. In the syntheses of microcarpalide listed above, all the groups employed the same diene esters except for the protecting groups. RCM of the substrates, whose 4-OH and 5-OH were protected with acetonide (18 and 38), proceeded smoothly in good yield but with moderate E/Z-selectivity (2:1), regardless of the protecting group of 10-OH. The conformational restraint tethered by acetonide may make both of the reacting sites cyclize easier. On the other hand, when 4-OH and 5-OH were protected as benzyl ether separately (24 and 32), the reaction proceeded with excellent E-selectivity. However, in these cases, the protecting group at C-10 had a great inuence on reactivity, that is, MEM protection aorded good yield, while benzyl protection resulted in poor conversion. Careful tuning of protective groups, especially at allylic positions, is necessary for stereoselective construction of medium-sized rings as above by RCM. Recently, Mohapatra et al. reported syntheses of 10-membered lactones by protecting group directed RCM.48) 3. Our synthesis of microcarpalide Our synthesis of microcarpalide is shown in Scheme 2 [6].49,50) Most synthetic approaches have been based on RCM, whereas we selected lactonization as a ring-closing step and Julia coupling51) for the construc-

tion of trans-olen. We also decided to introduce all four stereocenters using Sharpless AD.30,31) Starting from the known diol 45,52) olenic ester 46 was prepared by Claisen rearrangement,53,54) which was subjected to Sharpless AD. Enrichment of enantiomeric purity was achieved by recrystallization of an intermediate to give aldehyde 47 in an enantiomerically pure form. On the other hand, the sulfone unit was prepared by Sharpless AD of the known olenic alcohol 48,55) and sulfone 49 was also obtained in an enantiomerically pure form via recrystallization of an intermediate. One-pot Julia coupling51,56,57) of sulfone 49 and aldehyde 47 using KHMDS aorded olen 50 in good yield, but E/Z selectivity was not very high (E/Z = 2:1). Because the low selectivity appeared to be caused by some chelation eects of oxygen functional groups in sulfone 49 and aldehyde 47 with potassium cation, we tried other conditions employing additives to prevent this chelation. When 18-c-6 was added, trans-olen 50 was successfully obtained in good yield and high selectivity (E/Z = 10:1). After separation of 50 from cis-isomer, it was converted to the corresponding hydroxy acid, which was subjected to Yamaguchi lactonization14) to aord 10-membered lactone in excellent yield (94%). Formation of dimeric lactone was observed at higher concentrations, but not in 1 mM. Finally, deprotection was performed using BF3 OEt2 and (CH2 SH)2 at 10  C to give microcarpalide successfully. Thus we accomplished a convergent and stereoselective synthesis of microcarpalide with good eciency employing Julia coupling and Yamaguchi lactonization. Interestingly, acid-catalyzed isomerization of microcarpalide was claried in the course of our examination. Microcarpalide was found to be partially isomerized by treatment with TsOH, aording a mixture of microcarpalide (10-memberd lactone) and 51 (11-membered lactone) in a ratio 6.5:1.

4. Synthesis of microcarpalide by Kumar et al. In 2005, Kumar and co-workers reported another synthesis using Yamaguchi lactonization as a ringclosing step (Scheme 2 [6]).58) They also introduced all four stereocenters using Sharpless AD.30,31) Acetylene 53 was prepared from ,-unsaturated ester 52, which was obtained from 1,4-butanediol. Stereocenters were installed by Sharpless AD, and terminal acetylene was constructed by Corey-Fuchs protocol59) to give 53. Epoxide 55 was derived from allyl alcohol 54 via Sharpless AD, and Yamaguchi coupling60) of acetylene 53 and epoxide 55 provided alcohol 56. Coupled compound 56 was converted to hydroxy acid 57 by Birch reduction61) of the triple bond to trans-olen. Hydroxy acid 57 was the same intermediate as ours, and it was transformed into microcarpalide in a manner similar to our synthesis. Though the reaction scheme was slightly long, the yield of each step was very good.

III. Synthetic Approaches to Sch 642305

In 2003, Chu et al. isolated Sch 642305 from Penicillium verrucosum as a potent inhibitor of bacterial DNA primase.62) Because DNA primase is necessary for the replication of chromosomal DNA,63,64) this compound is thought to provide an alternative treatment for infectious diseases. In addition, Jayasuriya and co-

Syntheses of 10-Membered Lactones

[1] Marco et al. (2002) 10% in 9 steps from (R )-glycidol
OH OH O (R )-glycidol HO OH HO2C 17 Hexn 6 steps OMOM 16 O O CO2H lit. 25 HO2C (S,S )-tartaric acid esterification Hexn O O RCM O OMOM 18 Hexn O (E/Z = 67/33) 67% O OMOM Hexn O
9 10

975

O O
5

OH OH
4

19

O O OH Microcarpalide

[2] Gurjar et al. (2003) 8.7% in 16 steps from 22

Hexn 20 HO O 13 steps 22 OBn prepared fromD-mannose O O HO2C 23 Sharpless AD CO2Et 10 steps OH Hexn OMEM 21 OBn OBn esterification Hexn O OMEM O OBn OBn RCM Hexn (E/Z = 10/1) 67% O OMEM OBn OBn

B
O

24

25

[3] Davoli et al. (2004 and revised in 2005) 0.78% in 12 steps from pinanediol
Cl Hexn B O 3 steps Hexn B O 2 steps Hexn OBn 28 esterification Hexn OBn 3 steps HO2C 31 OBn OBn OH OBn OBn RCM O O Hexn O (E only) O OBn 26% 33 (57% of 32 recovered) OBn OBn

O 26 O R B O

OBn O 27 Matteson stereoselective homologation X2 OBn O R Cl B O 30

32

3 steps 29 R = CH2CH2CO2But

[4] Sharma and Cherukupalli (2006) 2.4% in 13 steps from 1,4-butanediol

O OH O 6 steps Hexn OBn 35 O OBn O HO2C 37 esterification Hexn OBn 38 O O RCM O Hexn O (E/Z = 67/33) 78% OBn 39 O O O

O 34 prepared from L-ascorbic acid O O N O OH

B
O

7 steps OPMB 36 Bn prepared from1,4-butanediol by Evans aldol

[5] Banwell and Loong (2004) 3.4% in 16 steps from (S )-malic acid
Hexn 40 OH HO2C CO2H 9 steps PMBO Sharpless AD OH 5 steps Hexn O O HO2C 42 41 O OH HO esterification 2 steps O O Hexn 43 O O MeO2C HornerO Emmons reaction Hexn 2 steps O crossO metathesis with CH2CH2 Hexn O O

O OMOM

O 44

(S )-malic acid

O O OMOM ent-18 same way as Marco's

[6] Our synthesis (2004 and revised in 2005) 18% in 13 steps from 48
Claisen rearrangement OH OH 45 2 steps MeO2C 46 Sharpless AD OH 48 8 steps 49 OMOM Sharpless AD OBn 5 steps MeO2C 47 O OTBS SO2PT O CHO Julia coupling Hexn
PT =
Ph N N N N

ent-B
O O OTBS OMOM 50 CO2Me HO Hexn O OO 51 Yamaguchi lactonization

B
4 steps OH OH

[7] Kumar et al. (2005) 28% in 17 steps from 1,4-butanediol

Sharpless AD PMBO CO2Et 6 steps Sharpless AD O 4 steps 54 55 OMOM PMBO 53 O 52 prepared from1,4-butanediol OH O Yamaguchi coupling Hexn O Birch reduction 5 steps Hexn OPMB O

O OH OMOM 57 CO2H

Yamaguchi lactonization

B
2 steps

OH OMOM 56

Scheme 2. Synthetic Approaches to Microcarpalide.

workers have reported that Sch 642305 potently inhibits HIV-1 Tat transactivation.65) Sch 642305 has a bicyclic structure including 10-membered lactone fused with 4-hydroxycyclohexenone. Its unique structure and its

signicant biological activities have attracted the attention of many organic chemists, and six synthetic approaches, including ours, have been reported in the past few years.

976

K. ISHIGAMI

1. First synthesis of Sch 642305 by Mehta and Shinde First synthesis of Sch 642305 was achieved by Mehta and Shinde in 2005 (Scheme 3 [1]).66) They employed the RCM protocol4) to construct a 10-membered lactone moiety, and they started from the known endo-tricyclic DielsAlder adduct 5867) of cyclopentadiene and pbenzoquinone. Asymmetric centers were introduced by lipase-mediated enzymatic desymmetrization68,69) of meso-diol,70,71) which was obtained by reduction of 58. After oxidation to cyclohexanone 59, zinc-mediated Barbier-type allylation and subsequent oxy-Cope rearrangement72) provided the allylated product as a single diastereomer. The norbornyl scaold was disengaged through a retro-Diels-Alder process to furnish cyclohexenone 60. An ester moiety was introduced by regioand stereoselective alkylation of 60, and the RCM precursor 61 was obtained via Luche reduction (C-4; / = 1.2:1).73) RCM of 61 with the 2nd-generation Grubbs catalyst20) proceeded smoothly to generate the bicyclic framework. Because it was dicult to reduce the double bond in the lactone ring selectively, catalytic hydrogenation led to fully saturated bicyclic compound 62, in which the enone had to be restored. The restoration was accomplished via the phenylselenationselenoxide elimination sequence,74) and nally deprotection with TBAF-AcOH aorded Sch 642305. In this approach, the selectivity of reduction at C-4 was not satisfactory, and the necessity of restoring the enone was a detour. 2. Our synthesis of Sch 642305 Following rst synthesis, our group also succeeded in stereoselective synthesis of Sch 642305 (Scheme 3 [2]).75) We selected lactonization as a ring-closing step and dianion alkylation for construction of the lactonization precursor. Our starting material 63 (99% ee) was prepared in large quantity via stereoselective reduction of the corresponding -ketoester with bakers yeast.76) In our laboratory, a number of natural products were successfully synthesized using 63 as a chiral building block.77) This chiral building block was converted to -ketosulfoxide 64 after elongation of the side chain. In the step introducing phenylthio group, regioselectivity was 3.5:1, and the undesired minor isomer was easily removed by chromatography after oxidation to 64. On the other hand, iodide 65 was obtained in several steps from (S)-3-hydroxybutylate (98% ee), which could be easily prepared in large amounts from ethyl acetoacetate via stereoselective reduction with bakers yeast and enzymatic improvement of the optical purity.78,79) Ketosulfoxide 64 was subjected to regio- and stereoselective alkylation with iodide 65 by the dianion procedure,8082) and subsequent thermal elimination aorded tri-substituted cyclohexenone 66 as a single isomer in moderate yield. As we expected, alkylation occurred selectively from the less hindered -face of the dianion. After conversion to hydroxy acid 67, it was subjected to Yamaguchi lactonization14) to aord 10-membered lactone successfully with a small amount of a dimeric lactone. Removal of the TBS group was successful using TBAF-AcOH as in Mehtas condition, while other conditions resulted in partial epimerization at the C-6 position (/ = 3:11:1). Thus we succeeded in stereoselective synthesis of Sch 642305

starting from two chiral sources, which were prepared by stereoselective reduction with bakers yeast. Alkylation of the -ketosulfoxide by dianion procedure selectively aorded the desired stereochemistry, and Yamaguchis lactonization was also successful in good yield. 3. Synthesis of Sch 642305 by Snider and Zhou Snider and Zhou also reported the synthesis of Sch 642305 employing Yamaguchi lactonization,14) but their approach was based on a biomimetic transannular Michael reaction83,84) of 14-membered lactone 71 (Scheme 3 [3]).85) Introduction of the chiral center was performed on olen 68 by Jacobsen kinetic resolution8689) using oligomeric (salen)Co(III) catalyst90) to give epoxide 69. After reductive opening of the epoxide, the resulting aldehyde was reacted with acetylide and converted to hydroxy acid 70. Though compound 70 was obtained as an inseparable 1:1 mixture of diastereomers, they were readily separated after the formation of macrolide 71 by Yamaguchi lactonization.14) Treatment of ketolactone 71 with NaH aorded transannular Michael adduct 72 as a single isomer in good yield, but this bicyclic compound had a cis-fused structure. Their MM2 calculations suggested that Sch 642305 was about 1 kcal/mol more stable than 6-epi-Sch 642305, and so they examined the epimerization of 72. The best result was obtained by microwave irradiation of 72 in the presence of TFA, which gave a separable mixture of 72 and the desired 6-epi-72 (2.7:1). Finally, deprotection of 6-epi-72 provided Sch 642305. In this synthesis, the stereoselectivity at C-4 and C-6 was not satisfactory, but the synthetic approach based on a biomimetic transannular Michael reaction was original and interesting. 4. Synthesis of Sch 642305 by Wilson and Trauner Wilson and Trauner reported the synthesis of Sch 642305 based on RCM (Scheme 3 [4]).91) Their approach was similar to Mehtas rst synthesis,66) but was a very concise synthesis in short steps, starting from the simple building block 73. Cyclohexenone 73 is known to be preparable from a natural product, quinic acid.92,93) Silyl ketene acetal 74, which was easily prepared from commercially available (S)-4-penten-2-ol, was subjected to Mukaiyama-Michael addition94) to enone 73 with concomitant silyl transfer to aord an inseparable 3.7:1 mixture of silyl enol ether 75 and its anti-isomer. Stereoselective allylation of 75 was successful by employing TASF95,96) to give cyclohexanone 76 diastereoselectively. RCM4) of the diene 76 with 2nd-generation Grubbs catalyst20) generated a bicyclic framework, and the newly formed double bond was reduced to bicyclic lactone 77. They stated that the corresponding anti-isomer was presumably lost at the RCM step. Finally, the enone moiety was constructed by SaegusaIto unsaturation,97) and deprotection completed the target molecule. Thus they succeeded in short-step synthesis of Sch 642305. 5. Synthesis of Sch 642305 by Carda et al. Carda et al. also succeeded in the short-step synthesis of Sch 642305 using cyclohexenone 7392,93) as the starting material. A methodology similar to Wilson s

Syntheses of 10-Membered Lactones

[1] Mehta and Shinde (2005) 4.3% in 19 steps from 58
O enzymatic desymmetrization 5 steps O 58 59 O oxy-Cope rearrangement O and retro-DA 3 steps OTBS O TBDPSO O 4 steps OTBS 60 OTBS 61 62 RCM and TBDPSO hydrogenation 4 steps O O O

977

C
3 steps

[2] Our synthesis (2006) 10% in 18 steps from chiral building block 63
HO CO2Et TBSO regio- and stereoselective alkylation TBSO OTES and elimination OTHP 2 steps PhS O O 64 65 O I 66 O TBSO OTES OTHP 4 steps O 67 CO2H HO Yamaguchi lactonization 2 steps O Sch 642305 HO
4 5 6

O 10 steps O 63

[3] Snider and Zhou (2006) 1.6% in 17 steps from 7-octenal

Jacobsen kinetic resolution O O 68 prepared from 7-octenal 2 steps RO O O O 69 6 steps O O 70 (/ = 1/1, inseparable) CO2H HO O Yamaguchi RO lactonization 2 steps O 71 R=TBDPS O 72 O transannular RO Michael addition O O epimerization (/ =1/2.7)

C
2 steps

[4] Wilson and Trauner (2006) 12% in 7 steps from enone 73

O HO HO HO2C OH lit. 92,93 32% in 6 steps Br O TBSO 73 O 74 OTBS 75 (syn/anti = 3.7/1, inseparable) O 76 2 steps O 77 3 steps OH TBSO Mukaiyama- TBSO Michael addition TBSO O O O RCM and TBSO hydrogenation O O Saegusa oxidation

quinic acid

[5] Carda et al. (2007) 12% in 8 steps from enone 73

TBSO MukaiyamaMichael addition TBSO lit. 99 OTBS O 73 78 OEt OTBS 79 O CO2Et TBSO CO2Et Mitsunobu TBSO lactonization OBn O 80 I 81 3 steps O 77 Ph O Saegusa oxidation

C
OBn 3 steps O O 3 steps Ph O O bromo- Ph etherification O lit. 104 Br 82 83 84 O 85 O OMe Ph O OTBDPS CHO O 86 Ph O OMe Ph O Ph O OMe
TBDOSO HO

[6] Fujioka et al. (2007) 3.5% in 11 steps from acetal 83

Ph Ph Ph Ph O 3 steps PhS O 87 O OMe
TBDOSO

Ph PhS O 88 2 steps

CO2H HO

CoreyMukaiyama lactonization

Scheme 3. Synthetic Approaches to Sch 642305.

synthesis91) was employed, except for ring-closure (Scheme 3 [5]).98) According to the reported procedure,99) cyclohexenone 73 was reacted with silyl ketene acetal 78100) to aord silyl enol ether 79 as the only product. Treatment of 79 with iodide 80 in the presence of TASF95,96) provided ester 81 as the sole stereoisomer. In the conversion of the ester 81 to the corresponding hydroxy acid, ethyl ester was hydrolyzed in the presence of potassium trimethylsilanolate101) to avoid epimerization at C-6. The hydroxy acid was subjected to Mitsunobu lactonization102) to give bicylic lactone 77. In the same manner as in Wilson s synthesis,91) bicyclic lactone 77 was converted to Sch 642305 via Saegusa-Ito unsaturation.97) They succeeded in concise synthesis, and the stereoselectivity was excellent.

6. Synthesis of Sch 642305 by Fujioka et al. Recently, Fujioka et al. reported the synthesis of Sch 642305 using chiral auxiliary multiuse methodology (Scheme 3 [6]).103) They used (R,R)-hydrobenzoin not only as a chiral auxiliary, but also as a protecting group and as a template to control regio- and stereochemistry. Bromo acetal 83 was synthesized by intramolecular bromoetherication of cyclohexadiene acetal 82.104) Hydroboration of 83 using thexylborane was followed by oxidation to give a -bromoketone, from which spontaneous elimination aorded enone 84 in moderate yield. While direct alkylation at the 0 -position of enone 84 was unsuccessful, aldol reaction of 84 with 85 occurred from a less hindered face of the cyclohexenone ring to give 86 in the diastereomerically pure form. After

978

K. ISHIGAMI 4) 5) 6) 7) 8) 9) 10) Nicolaou KC, Bulger PG, and Sarlah D, Angew. Chem. Int. Ed., 44, 44904527 (2005), and references cited therein. Papendorf O, Ko nig GM, Wright AD, Chorus I, and Oberemm A, J. Nat. Prod., 60, 12981300 (1997). Stierle DB, Stierle AA, Bugni T, and Loewen G, J. Nat. Prod., 61, 251252 (1998). Ishigami K, Motoyoshi H, and Kitahara T, Tetrahedron Lett., 41, 88978901 (2000). Motoyoshi H, Ishigami K, and Kitahara T, Tetrahedron, 57, 38993908 (2001). Wong MYH and Gray GR, J. Am. Chem. Soc., 100, 3548 3553 (1978). Blanchette MA, Choy W, Davis JT, Essenfeld AP, Masamune S, Roush WR, and Sakai T, Tetrahedron Lett., 25, 21832186 (1984). Corey EJ, Bakshi RK, and Shibata S, J. Am. Chem. Soc., 109, 55515553 (1987). Corey EJ and Helal CJ, Angew. Chem. Int. Ed., 37, 19872012 (1998). Ohtani I, Kusumi T, Kashman Y, and Kakisawa H, J. Am. Chem. Soc., 113, 40924096 (1991). Inanaga J, Hirata K, Saeki H, Katsuki T, and Yamaguchi M, Bull. Chem. Soc. Jpn., 52, 19891993 (1979). Corey EJ and Nicolaou KC, J. Am. Chem. Soc., 96, 5614 5616 (1974). Yadav JS, Somalah R, Ravindar K, and Chandraiah L, Tetrahedron Lett., 49, 28482850 (2008). Katsuki T and Sharpless KB, J. Am. Chem. Soc., 102, 5974 5976 (1980). Marshall JA and Johns BA, J. Org. Chem., 65, 15011510 (2000). Blackwell HE, OLeary DJ, Chatterjee AK, Washenfelder RA, Bussmann DA, and Grubbs RH, J. Am. Chem. Soc., 122, 5871 (2000), and references cited therein. Scholl M, Ding S, Lee CW, and Grubbs RH, Org. Lett., 1, 953956 (1999). Ratnayake AS, Yoshida WY, Moonberry SL, and Hemscheidt T, Org. Lett., 3, 34793481 (2001). Murga J, Falomir E, Garcia-Fortanet J, Carda M, and Marco JA, Org. Lett., 4, 34473449 (2002). Garcia-Fortanet J, Murga J, Falomir E, Carda M, and Marco JA, J. Org. Chem., 70, 98229827 (2005). Nishigaichi Y, Takuwa A, Naruta Y, and Maruyama K, Tetrahedron, 49, 73957426 (1993). Batty D and Crich DJ, J. Chem. Soc., Perkin Trans. 1, 3193 3204 (1992). Schwab P, France MB, Ziller JW, and Grubbs RH, Angew. Chem. Int. Ed., 34, 20392041 (1995). Fu rstner A, Radkowski K, Wirtz C, Goddard R, Lehmann CW, and Mynott R, J. Am. Chem. Soc., 124, 70617069 (2002). Gurjar MK, Nagaprasad R, and Ramana CV, Tetrahedron Lett., 44, 28732875 (2003). Gurjar MK, Nagaprasad R, Ramana CV, Karmakar S, and Mohapatra DK, ARKIVOC, 237257 (2005). Sharpless KB, Amberg W, Bennani YL, Crispino GA, Hartung J, Jeong K-S, Kwong H-L, Morikawa K, Wang Z-M, Xu D, and Zhang X-L, J. Org. Chem., 57, 27682771 (1992). Zaitsev AB and Adolfsson H, Synthesis, 17251756 (2006), and references cited therein. Moore BS, Cho H, Casati R, Kennedy E, Reynolds KA, Mocek U, Beale JM, and Floss HG, J. Am. Chem. Soc., 115, 52545266 (1993). Coutrot P, Grison C, and Lecouvey M, Bull. Soc. Chim. Fr., 134, 2745 (1997). Ghosh S, Rao RV, and Shashidhar J, Tetrahedron Lett., 46, 54795481 (2005). Davoli P, Spaggiari A, Castagnetti L, and Prati F, Org. Biomol. Chem., 2, 3847 (2004). Davoli P, Fava R, Morandi S, Spaggiari A, and Prati F, Tetrahedron, 61, 44274436 (2005). Matteson DS, Acc. Chem. Res., 21, 294300 (1988), and references cited therein.

Michael addition of PhSH to the enone moiety, the secondary hydroxy group was removed by reduction of the corresponding xanthate to aord ketone 87. This ketone was partially deprotected, and was transformed into hydroxy acid 88. Macrolactonization was performed by the modied Corey-Mukaiyama method.15) During this lactonization, -elimination of PhSH occurred simultaneously to regenerate the enone moiety, and removal of the chiral source provided Sch 642305. Though, chemical yields in some steps were not high, application of the multipurpose chiral auxiliary was interesting and control of regio- and stereochemistry was satisfactory.

11)

IV. Conclusion
We have briey discussed synthetic studies on three natural 10-membered lactones, mueggelone, microcarpalide, and Sch 642305. Because of their potent activities and their unique structures, these microbial metabolites have fascinated many synthetic chemists, and a number of synthetic approaches have been reported, as described above. Now RCM is the order of the day, and many approaches to these macrolides employ RCM as a ring-closing reaction. In the synthesis of medium-sized lactones, E/Z selectivity and reactivity are greatly inuenced by the structure of the product or substrate, and thus it is important to tune up the intermediate of the synthesis. On the other hand, Yamaguchi lactonization is one of the classical methodologies, but it continuously exists as a powerful method for the synthesis of macrolide. RCM and Yamaguchi lactonization are alternative and complementary ways in the synthesis of this class of compounds. Inspired by the unique structures and potent activities of natural products, organic chemists will continue to make progress in the synthesis of natural products. It is desirable that synthetic studies on natural products make a contribution to the development of both chemistry and biology.

12) 13) 14) 15) 16) 17) 18) 19)

20) 21) 22) 23) 24) 25) 26) 27)

Acknowledgments
I thank Emeritus Professor Kenji Mori (The University of Tokyo), Emeritus Professor Takeshi Kitahara (The University of Tokyo), Emeritus Professor Haruo Seto (The University of Tokyo), and Professor Hidenori Watanabe (The University of Tokyo) for continuous encouragement and for many fruitful discussions on my research. These studies were partially supported by a Grant-in-Aid for Scientic Research from the Japanese Ministry of Education, Culture, Sports, Science, and Technology. I also thank the Japan Society for Bioscience, Biotechnology, and Agrochemistry for the Japan Bioscience, Biotechnology, and Agrochemistry Society Award for the Encouragement of Young Scientists.

28) 29) 30)

31) 32)

33) 34) 35) 36) 37)

References
1) 2) 3) Naves YR and Grampolo AV, Helv. Chim. Acta, 25, 1500 1514 (1942). Demole E, Willhalm B, and Stoll M, Helv. Chim. Acta, 47, 11521159 (1964). Ishida T and Wada K, J. Chem. Soc., Chem. Commun., 209 210 (1975).

Syntheses of 10-Membered Lactones 38) 39) 40) 41) 42) 43) 44) 45) 46) 47) 48) Matteson DS, Chem. Rev., 89, 15351551 (1989), and references cited therein. Matteson DS, J. Organomet. Chem., 581, 5165 (1999), and references cited therein. Matteson DS, Sadhu KM, and Peterson ML, J. Am. Chem. Soc., 108, 810819 (1986). Prasad KR, Penchalaiah K, Choudhary A, and Anbarasan P, Tetrahedron Lett., 48, 309311 (2007). Sharma GVM and Cherukupalli GR, Tetrahedron: Asymmetry, 17, 10811088 (2006). Jones TK, Reamer RA, Desmond R, and Mills SG, J. Am. Chem. Soc., 112, 29983017 (1990). Banwell MG and Loong DTJ, Heterocycles, 62, 713734 (2004). Chavan SP and Praveen C, Tetrahedron Lett., 46, 19391941 (2005). Fu rstner A, Nagano T, Mu ller C, Seidel G, and Mu ller O, Chem. Eur. J., 13, 14521462 (2007). Pandit UK, Overkleeft HS, Borer BC, and Bieraugel H, Eur. J. Org. Chem., 959968 (1999). Mohapatra DK, Ramesh DK, Giardello MA, Chorgade MS, Gurjar MK, and Grubbs RH, Tetrahedron Lett., 48, 2621 2625 (2007). Ishigami K and Kitahara T, Heterocycles, 63, 785790 (2004). Ishigami K, Watanabe H, and Kitahara T, Tetrahedron, 61, 75467553 (2005). Baudin JB, Hareau G, Julia SA, and Ruel O, Tetrahedron Lett., 32, 11751178 (1991). Rao AVR, Bose DS, Gurjar MK, and Ravindranathan T, Tetrahedron, 45, 70317040 (1989). Johnson WS, Werthemann L, Bartlett WR, Brocksom TJ, Li T-T, Faulkner DJ, and Petersen MR, J. Am. Chem. Soc., 92, 741743 (1970). Wipf P and Lim S, J. Am. Chem. Soc., 117, 558559 (1995). Schlosser M, Tuong HB, and Schaub B, Tetrahedron Lett., 26, 311314 (1985). Blakemore PR, Cole WJ, Kocienski PJ, and Morley A, Synlett, 2628 (1998). Blakemore PR, J. Chem. Soc., Perkin Trans. 1, 25632585 (2002), and references cited therein. Kumar P and Naidu SV, J. Org. Chem., 70, 42074210 (2005). Corey EJ and Fuchs PL, Tetrahedron Lett., 37693772 (1972). Yamaguchi M and Hirao I, Tetrahedron Lett., 24, 391 394(1983). Schon I, Chem. Rev., 84, 287297 (1984), and references cited therein. Chu M, Mierzwa R, Xu L, He L, Terracciano J, Patel M, Gullo V, Black T, Zhao W, Chan T-M, and McPhail AT, J. Nat. Prod., 66, 15271530 (2003). Bouche JP, Zechel K, and Kornberg A, J. Biol. Chem., 250, 59956001 (1975). Arai KI and Kornberg A, Proc. Natl. Acad. Sci. USA, 76, 43084312 (1979). Jayasuriya H, Zink DL, Polishook JD, Bills GF, Dombrowski AW, Genilloud O, Pelacz FF, Herranz L, Quamina D, Lingham RB, Danzeizem R, Graham PL, Tomassini JE, and Singh SB, Chem. Biodiversity, 2, 112122 (2005). Mehta G and Shinde HM, Chem. Commun., 37033705 (2005). Cookson RC, Grundwell E, and Hudec J, Chem. Ind., 1003 1004 (1958). Takano S, Higashi Y, Kamikubo T, Moriya M, and Ogasawara K, Synthesis, 948950 (1993). Konno H and Ogasawara K, Synthesis, 11351140 (1999). Wilson KE, Sediner RT, and Masamune S, J. Chem. Soc., Chem. Commun., 213214 (1970). 71) 72) 73) 74) 75) 76) 77) 78) 79) 80) 81) 82) 83) 84) 85) 86) 87)

979

49) 50) 51) 52) 53)

54) 55) 56) 57) 58) 59) 60) 61) 62)

88) 89) 90) 91) 92) 93) 94) 95) 96) 97) 98) 99) 100) 101) 102) 103) 104)

63) 64) 65)

66) 67) 68) 69) 70)

Marchand AP, LaRoe WD, Sharma GVM, Suri SC, and Reddy DS, J. Org. Chem., 51, 16221625 (1986). Wilson SR, Org. React., 43, 93250 (1993), and references cited therein. Gemal AL and Luche JL, J. Am. Chem. Soc., 103, 54545459 (1981). Reich HJ, Renga JM, and Reich IL, J. Am. Chem. Soc., 97, 54345447 (1975). Ishigami K, Katsuta R, and Watanabe H, Tetrahedron, 62, 22242230 (2006). Kitahara T and Mori K, Tetrahedron Lett., 26, 451452 (1985). Tachihara T and Kitahara T, Tetrahedron, 59, 17731780 (2003), and references cited therein. Sugai T, Fujita M, and Mori K, Nippon Kagaku Kaishi (in Japanese), 13151321 (1983). Sugai T and Ohta H, Agric. Biol. Chem., 53, 20092010 (1989). Grieco PA and Pogonowski CS, J. Chem. Soc., Chem. Commun., 7273 (1975). Walts AE and Roush WR, Tetrahedron, 41, 34633478 (1985). Avery MA, Chong KM, and Jennings-White C, J. Am. Chem. Soc., 114, 974979 (1992). Shimizu I and Nakagawa H, Tetrahedron Lett., 33, 49574958 (1992). Matsuura T and Yamamura S, Tetrahedron Lett., 41, 4805 4809 (2000). Snider BB and Zhou J, Org. Lett., 8, 12831286 (2006). Tokunaga M, Larrow JF, Kakiuchi F, and Jacobsen EN, Science, 277, 936938 (1997). Schaus SE, Brandes BD, Larrow JF, Tokunaga M, Hansen KB, Gould AE, Furrow ME, and Jacobsen EN, J. Am. Chem. Soc., 124, 13071315 (2002). Ready JM and Jacobsen EN, Angew. Chem. Int. Ed., 41, 13741377 (2002). Nielsen LPC, Stevenson CP, Blackmond DG, and Jacobsen EN, J. Am. Chem. Soc., 126, 13601362 (2004). White DE and Jacobsen EN, Tetrahedron: Asymmetry, 14, 36333638 (2003). Wilson EM and Trauner D, Org. Lett., 9, 13271329 (2007). Trost BM and Romero AG, J. Org. Chem., 51, 23322342 (1986). Audia JE, Boisvert L, Patten AD, Villalobos A, and Danishefsky SJ, J. Org. Chem., 54, 37383740 (1989). Kobayashi S and Mukaiyama T, Chem. Lett., 18051808 (1986). Noyori R, Nishida I, and Sakata J, Tetrahedron Lett., 21, 20852088 (1980). Noyori R, Nishida I, and Sakata J, J. Am. Chem. Soc., 105, 15981608 (1983). Ito Y, Hirao T, and Saegusa T, J. Org. Chem., 43, 10111013 (1978). a-Fontanet J, Carda M, and Marco JA, Tetrahedron, 63, Garc 1213112137 (2007). Danishefsky SJ and Simoneau B, J. Am. Chem. Soc., 111, 25992604 (1989). Kita Y, Segawa J, Haruta J, Yasuda H, and Tamura Y, J. Chem. Soc., Perkin Trans. 1, 10991104 (1982). Laganis ED and Chenard BL, Tetrahedron Lett., 25, 5831 5834 (1984). Kurihara T, Nakajima Y, and Mitsunobu O, Tetrahedron Lett., 17, 24552458 (1976). Fujioka H, Ohba Y, Nakahara K, Takatsuji M, Murai K, Ito M, and Kita Y, Org. Lett., 9, 56055608 (2007). Fujioka H, Kotoku N, Sawama Y, Nagatomi Y, and Kita Y, Tetrahedron Lett., 43, 48254828 (2002).