SPOTLIGHT

137

SYNLETT

Spotlight 418
This feature focuses on a reagent chosen by a postgraduate, highlighting the uses and preparation of the reagent in current research

spotlight Manganese(III) Acetate Compiled by Manoj Mondal

Manoj Mondal was born in Roing, Arunachal Pradesh, India, in 1986. He received his MSc degree in Organic Chemistry in 2010 from Dibrugarh University. He then joined Dr. U. Boras research group at Dibrugarh University to pursue his PhD studies. His research interests focus on the synthesis of palladium- and copperbased catalysts for carboncarbon, carbonheteroatom bond-formation reactions. Department of Chemistry, Dibrugarh University, Dibrugarh 786004, India E-mail: manojjmondal@gmail.com Dedicated to my honourable mentor Dr. Utpal Bora
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Introduction
Manganese(III) acetate [Mn(OAc)3]-mediated free-radical reactions have emerged as important synthetic methods. Manganese acetate can be used as an oxidizing and chlorinating agent1 and in some cases in alkylations1 and inter- and intramolecular cyclizations.2 Due to the poor solubility of Mn(OAc)3 in common organic solvents, Mn(OAc)3-mediated reactions are often carried out in acetic acid, although other solvents including toluene, alcohols, acetonitrile, dichloromethane and chlorobenzene

can be used.3 Mn(OAc)3 promotes the synthesis of many alkaloids,4 triterpenes,5 and drugs.6 Mn(OAc)3 is commercially available in form of its dehydrate as a brown powder and can be prepared in the laboratory7 by adding KMnO4 to a pre-heated mixture of Mn(OAc)2 and glacial acetic acid (Scheme 1). Addition of acetic anhydride to the reaction produces the anhydrous form.8
110 C Mn(OAc)2 + AcOH + KMnO4 20 min Mn(OAc)3 + AcOK + MnO2

Scheme 1 Preparation of manganese (III) acetate

Abstracts
(A) Catalytic amount of manganese acetate in glacial acetic acid oxidizes 3-alkyl-substituted 2,4-pyrrolidinediones to their corresponding 3-hydroperoxy derivatives. This procedure leads to a new type of heterocyclic hydroperoxides.9
R2 O N R1 R1, R2 = Ar, Alk Mn(OAc)3 AcOH, r.t. air, 9099% O N R1 up to 99% yield
+

R2 HO

OOH O

(B) Manganese acetate-mediated oxidative cyclisation of alkyl substituted 2-[2-(N-arylamino)-2-oxoethyl]malonates yields the corresponding substituted 4,4-bis(ethoxycarbonyl)-3,4-dihydro-2(1H)quinolinones in good to excellent yield (4697%).4c

CO2Et R2 CO2Et N R1 O Mn(OAc)3 AcOH,

EtO2C

CO2Et R2 N R1 O

(C) Manganese acetate generates aryl radicals or cations when reacted with aryl boronic acids10a,b or aryl hydrazines10c preferentially in aromatic solvents (benzene, thiophene) and subsequently leads to the formation of biaryls under microwave,10a room temperature,10b and reflux10c conditions. (D) When a catalytic amount of manganese acetate is added to a stirred solution of alkyl- or aryl-substituted alcohol and acetic acid, acetylation occurs quantitatively (99% yield) within two hours at reflux.11

B(OH)2 Mn(OAc)3 (3 equiv) R PhH R

NHNH2HCl Mn(OAc)3 (3 equiv) PhH R

OH

Mn(OAc)3 AcOH, 99% yield

OAc

SYNLETT 2013, 24, 01370138 Advanced online publication: 04.12.20120936-52141437-2096 DOI: 10.1055/s-0032-1317531; Art ID: ST-2012-V0425-V Georg Thieme Verlag Stuttgart New York

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M. Mondal

SPOTLIGHT

(E) Manganese acetate can be used as an effective and mild oxidizing agent for the regeneration of carbonyl compounds from their corresponding oximes in good yield (8696%). This reaction condition can tolerate many functional groups, e.g. alkyl and aryl oximes.12 (F) Oxidative ring expansion of substituted 9H-xanthene 1 in the presence of manganese acetate gives 9- or 10-dibenz[b,f]oxepincarboxylates 2 in good yield. When R1 = Me and R2 = 1-OMe, this reaction gives two regioisomers. Otherwise the reaction is highly regioselective. It was proposed that the process for the formation of the product must include a 1,2-aryl radical rearrangement followed by an oxidative decarboxylation.4b

R1 NOH R2

Mn(OAc)3 (1 equiv) benzene, 30120 min

R1 O R2

MnII R1O2C O CO2H Mn(OAc)3 R1O2C AcOHH2O (9:1) R2 R1 = Me, Et, i-Pr R2 = H, OMe O O O

MnIII CO2R1

MnIII 1,2-aryl radical rearrangment R2

O 1

O R2 2 (6385% yield)

O O

Mn(OAc)3

+ R1 2

O 1 R1, R2 = Ar, Alk

OH 3 up to 80% yield

OH

4 up to 97% yield

(H) Manganese acetate can be employed as an oxidant for the regeneration of 2,3-dichloro-5,6-dicyanoquinone (DDQ) from the corresponding hydroquinone (HDDQ). This DDQ-regeneration technique using manganese acetate (3 equiv) and DDQ (10 mol%), can be applied to the deprotection of p-methoxy benzyl (PMB) ethers.14

Mn(OAc)3 R HO alcohol Me O PMB ether OR DDQ Mn(OAc)2 HDDQ 2 AcOH Cl CH2Cl2, r.t. Cl

OAc O MnIII OAc CN CN O MnIII OAc OAc

(I) Manganese acetate-promoted oxidative free-radical condensation reaction of phosphate ester(dialkylphosphate) with alkynes15 yields the corresponding indenones 1 and direct phosphonylation of arenes6 yields regioselectively dialkylphosphonates 2.

R1 R1 O R2 P(OR)2 2 8595% yield R2 O H P(OR)2 60 C O Ar Ph PO(OR)2 Ar 1 6679% yield O

+ PhMe Mn(OAc)3 (3 equiv) air AcOH 6080 C

References
(1) Pan, X.-Q.; Zou, J.-P.; Zhang, W. Mol. Divers. 2009, 13, 421. (2) (a) Curran, D. P. Synthesis 1988, 489. (b) Jasperse, C. P.; Curran, D. P.; Fevig, T. L. Chem. Rev. 1991, 91, 1237. (3) (a) Wang, G. W.; Dong, Y. W.; Wu, P.; Yuan, T. T.; Shen, Y. B. J. Org. Chem. 2008, 73, 7088. (b) Snider, B. B. Chem. Rev. 1996, 96, 339. (4) (a) Wang, X.; Ma, Z.; Lu, J.; Tan, X.; Chen, C. J. Am. Chem. Soc. 2011, 133, 15350. (b) Cong, Z.; Miki, T.; Urakawa, O.; Nishino, H. J. Org. Chem. 2009, 74, 3978. (c) Tsubusaki, T.; Nishino, H. Tetrahedron 2009, 65, 9448. (5) Demir, A. S.; Gross, R. S.; Dunlap, N. K.; Hashemi, A. B.; Watt, D. S. Tetrahedron Lett. 1986, 27, 5567. (6) Xu, W.; Zou, J.-P.; Zhang, W. Tetrahedron Lett. 2010, 51, 2639. (7) Heiba, E. I.; Dessau, R. M.; Kolhl, W. J. Jr. J. Am. Chem. Soc. 1969, 91, 138. (8) Snider, B. B. Manganese(III) Acetate, In Encyclopedia of Reagents for Organic Synthesis; 2001, DOI: 10 1002/ 047084289X.rm018. (9) Haque, M. A.; Nishino, H. Synth. Commun. 2012, 42, 608. (10) (a) Demir, A. S.; Findik, H.; Saygili, N.; Subasi, N. T. Tetrahedron 2010, 66, 1308. (b) Demir, A. S.; Reis, O.; Emrullahoglu, M. J. Org. Chem. 2003, 68, 578. (c) Demir, A. S.; Reis, O.; Karaaslan, E. O. J. Chem. Soc., Perkin Trans. 1 2001, 3042. (11) Gowda, S.; Rai, K. M. L. J. Mol. Cat. A: Chem. 2004, 217, 27. (12) Demir, A. S.; Tanyeli, C.; Altinel, E. Tetrahedron Lett. 1997, 38, 7267. (13) Haque, M. A.; Nishino, H. Heterocycles 2011, 83, 1783. (14) Sharma, G. V. M.; Lavanya, B.; Mahalingam, A. K.; Krishna, P. R. Tetrahedron Lett. 2000, 41, 10323. (15) Pan, X.-Q.; Zou, J.-P.; Zhang, G.-L.; Zhang, W. Chem. Commun. 2010, 46, 1721.

Synlett 2013, 24, 137138

Georg Thieme Verlag Stuttgart New York

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(G) Under manganese acetate-catalyzed aerobic oxidation conditions in glacial acetic acid, tetronic acid 1 reacts with 1,1-disubstituted alkenes 2 (R1, R2 = Alk, Ar) to yield hydroperoxyethyl peroxylactones 3, while a similar reaction using 3-alkyl-substituted tetronic acid gives stable, crystalline peroxylactone 4 in good to excellent yield.13

R2 OOH R2 R1 R1 O R3 = H R2 HO R3 R2
1 3 O R = alkyl R O O Mn(OAc)3

R3 O O