Article

pubs.acs.org/Organometallics

Homogeneous Hydrogenation of Fatty Acid Methyl Esters and

Natural Oils under Neat Conditions
Neil T. Fairweather,*, Michael S. Gibson, and Hairong Guan*,

Procter & Gamble Company, 11510 Reed Hartman Highway, Cincinnati, Ohio 45241, United States

Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221, United States

ABSTRACT: A series of ruthenium- and iron-based pincer

catalysts have been tested for the homogeneous hydrogenation of
fatty acid methyl esters to fatty alcohols with turnover numbers
(TONs) of up to 1860. These catalysts operate under neat
conditions (no solvent) from the gram to the kilogram scale. The
required temperature (135 C) and H2 pressure (3001000 psig)
are much lower than those needed for current industrial
processes, which rely on heterogeneous copper chromite catalysts.
The fatty alcohol products can be puried through distillation,
resulting in low levels of Ru (1 ppm) and P (<25 ppm). The ve-
coordinate Milstein catalyst and Takasagos borane-stabilized
catalyst are also eective for the direct hydrogenation of coconut oil to fatty alcohols. These results hold the promise of using
homogeneous catalysts for ester hydrogenation in an industrial setting.

INTRODUCTION
The hydrogenation of fatty acid methyl esters (FAMEs) to
produce fatty alcohols is conducted industrially on a multi-
million ton scale each year for a variety of applications. Relevant
to the business at the Procter and Gamble Co. (P&G) is the
subsequent use of the fatty alcohols as surfactant precursors.
Our current process involves the hydrogenation of FAMEs
through a heterogeneous copper chromite catalyst that operates
at high temperature (250300 C) and H2 pressure (2000
3000 psig).1 Because the process under these conditions has
been run continuously for almost 50 years within P&G, we are
keenly aware of the high energy and capital costs associated
with the process. As such, we decided to embark on a research
program directed to understand what the hydrogenation plant
of the future may look like.
Homogeneous hydrogenation has been investigated in many
areas and often shows benets in terms of selectivity and the
ability to run under much milder conditions.2 An early report of
homogeneous hydrogenation of esters appeared in 19973 with
seminal publications appearing from both the Milstein group4
and Firmenich SA5 in 2006. Both catalytic systems are
ruthenium-based and feature multidentate ligands that are
capable of operating under much milder conditions (115 C
and 63 psig of H2 with the Milstein catalyst, 60100 C and
130710 psig of H2 with the Firmenich catalysts) for the
substrates examined. Since that time, many additional reports
describing homogeneous ester hydrogenation catalysts have
appeared from the groups of Milstein,6 Bergens,7 Morris,8
Song,9 Clark,10 Ikariya,11 Gusev,12 Beller,13 and Zhou,14 as well
as Takasago International Corp..15 Very recently, homogeneous
hydrogenation of esters using an iron-based catalyst has been
accomplished by Milstein,16 Beller,17 and us.18 Of the catalytic
systems reported to date, there are limitations that would
preclude their ability to be applied in a large industrial setting.
Some of these limitations include the following.
(1) Most incorporate precious metals such as ruthenium,
osmium, and iridium, resulting in higher cost and limited
commercial availability.
(2) Most of the reported examples were run only on a small
scale,19 and many are limited to uorinated or aromatic esters,
which are in general more reactive than FAMEs.
(3) Most catalytic systems use an exogenous solvent20 that
would signicantly increase the cost of the hydrogenation
process.
With this background, we decided to investigate if
homogeneous hydrogenation should be envisioned as a future
option for the industrial scale production of fatty alcohols. We
have focused our studies on the hydrogenation of two coconut
oil derived samples, CE-1295 and CE-1270. CE-1295 is
primarily methyl laurate (C12, 95%) with 2% methyl
decanoate (C10), 2% methyl myristate (C14), and 1%
C8/C16 methyl esters. CE-1270 consists of methyl laurate
(C12, 73%), methyl myristate (C14, 26%), and a small amount
of C10 and C16 methyl esters (1%).21 Through this work we
will demonstrate that Ru- or Fe-catalyzed homogeneous
hydrogenation of FAMEs can be carried out under neat
conditions. We will also report the direct hydrogenation of
coconut oil to fatty alcohols without conversion to FAMEs rst.
Received: November 10, 2014
Published: December 18, 2014

2014 American Chemical Society 335 dx.doi.org/10.1021/om5011337 | Organometallics 2015, 34, 335339
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Article

RESULTS AND DISCUSSION
Hydrogenation of CE-1295 on the Gram Scale. Our
studies commenced following a published procedure4 using the
ve-coordinate Ru(II) PNN-pincer catalyst (1 in Chart 1),
Chart 1. Ester Hydrogenation Catalysts Described in This
Study
which was originally developed by Milstein and currently is
commercially available. Hydrogenation of CE-1295 (typically
1.61.7 g) catalyzed by 1 (1.3 mol % catalyst loading) was
carried out in a 22 mL Parr reactor. At 115 C under 100 psig
of H2 pressure with 1,4-dioxane as the solvent, the desired fatty
alcohols were obtained in 97% combined GC yield within 7 h
(entry 1, Table 1). While this result is encouraging, the use of
1,4-dioxane as a reaction solvent is undesirable from both a cost
and environmental perspective when operating on scale. A
series of experiments (entries 28) showed that when the H2
pressure was increased to 300 psig and the temperature raised
to 135 C, the reaction could be run under neat conditions (no
exogenous solvent), yielding 96% of the fatty alcohols in only 1
h (entry 7). A similar yield was achieved with a lower catalyst
loading (0.7 mol %), but the H2 pressure had to be raised to
500 psig and the reaction mixture was stirred for 3 h (entry 9).
Although these results demonstrated the feasibility of employ-
ing the Milstein catalyst 1 for the hydrogenation of FAMEs, the
air and moisture stability of the catalyst was less than desirable.
A signicant drop in the activity of the catalyst was observed
after multiple reactions from the same catalyst sample due to
exposure to air from opening of the bottle. The more stable
Milstein catalyst precursor 2 was then tested in the presence of
a base, which is required to generate the active catalyst in situ.
Under reaction conditions similar to those described above
with the addition of powdered sodium methoxide (2.3 equiv
per Ru), the fatty alcohols were obtained in 44% yield after 24 h
(entry 10). Interestingly, switching the base from the solid form
to a solution in MeOH resulted in 92% of the fatty alcohols in
only 3 h (entry 11). It is unclear at this time if the increase in

Table 1. Catalytic Hydrogenation of CE-1295 in a 22 mL Parr Reactor

entry catalyst cat. loading (mol %) solvent base temp (C) pH2 (psig) time (h) alcohol yield (%)h
1 1 1.3 1,4-dioxanef N/A 115 100 7 97
2a 1 0.6 neat N/A 115 100 7 15
3 1 1.4 neat N/A 135 300 24 97
4 1 1.4 neat N/A 135 300 5 98
5 1 1.2 neat N/A 135 300 3 92
6 1 1.5 neat N/A 135 300 2 98
7 1 1.3 neat N/A 135 300 1 96
8 1 0.5 neat N/A 135 300 3 90
9 1 0.7 neat N/A 135 500 3 97
10 2 1.2 neat NaOMeg 135 300 24 44
11 2 1.2 neat NaOMe 135 300 3 92
12 2 1.2 neat NaOMe 135 750 1 98
13b 2 0.5 neat NaOMe 135 750 5 96
14c 3 0.4 THFf NaOMeg 100 300 24 24
15 3 1.1 neat NaOMeg 135 750 3 88
16 3 1.1 neat NaOMe 135 750 3 98
17 3 1.1 neat NaOMe 135 750 20 98
18 3 1.0 neat NaOMe 135 750 3 98
19 3 1.0 neat NaOMe 135 750 1 98
20 3 0.9 neat NaOMe 135 750 0.25 98
21b 3 0.5 neat NaOMe 135 750 1 97
22b 3 0.5 neat NaOMe 135 750 2 98
23d 3 0.3 neat NaOMe 135 750 21 98
24 4 1.0 neat N/A 135 750 3 98
25 4 0.9 neat N/A 135 750 1 98
26 5 1.0 neat NaOMe 135 750 7 98
27 5 1.0 neat NaOMe 135 750 3 97
28 6 1.0 neat NaOMe 135 750 24 79
29 6 1.0 THFf NaOMeg 135 750 3 96
30e 7 1.0 neat N/A 135 750 3 99
31e 7 1.2 neat N/A 135 750 1 96

a
5.0 g of CE-1295. b3.3 g of CE-1295. c1.1 g of CE-1295. d5.7 g of CE-1295. eReported in ref 18 for the hydrogenation of CE-1270. f4 mL of solvent
was used. gPowdered NaOMe was used. For all other experiments, a solution of NaOMe in MeOH (25 wt %) was used. hCombined GC yield for
the fatty alcohols.

336 dx.doi.org/10.1021/om5011337 | Organometallics 2015, 34, 335339

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yield is due merely to increased solubility of NaOMe in the Table 2. Catalytic Hydrogenation of CE-1270 at 135 C in a
methyl esters or if the added MeOH is serving as a solvent 300 mL Parr Reactor
facilitating the reaction. Increasing the H2 pressure from 300 to
alcohol
750 psig yielded more alcohols in a shorter time (entry 12), and yield (%)
the catalyst loading could be reduced to 0.5 mol % without
cat. loading (mol nNaOMe/ pH2
compromising the yield (entry 13). entry catalyst %) nRu (psig) 1h 3h
Under the conditions found to be eective when using either
1 3 0.55 8.5 750 98 99
Milstein catalyst (1 or 2, neat methyl esters, 1 mol % catalyst, 2 3 0.27 9.0 750 98 99
300 psig, 135 C), Takasagos commercially available Ru- 3 3 0.27 9.0 500 98 98
MACHO catalyst 3 showed signicantly less activity. Even with 4 3 0.27 8.9 250 77 91
THF as the solvent (0.4 mol % catalyst, 300 psig H2, 100 C), a 5 3 0.13 9.2 500 97 98
24 h reaction produced only 24% of the desired alcohols (Table 6 3 0.13 9.2 500 98 99
1, entry 14) vs >90% for the Milstein catalysts. Increasing the 7 3 0.07 9.6 750 91 97
H2 pressure to 750 psig resulted in 88% of the desired alcohols 8 3 0.07 9.5 500 92 98
with powdered NaOMe and 98% with NaOMe in MeOH 9 3 0.03 10.0 1000 10 11
(entries 15 and 16). In fact, under the higher-pressure 10a 3 0.14 8.9 500 94 98
conditions, a yield of 98% was achieved in only 15 min 11b 3 0.14 8.8 500 97 99
(entries 1720)! Lowering the catalyst loading to 0.3 mol % 12 4 0.26 N/A 750 86 91
was feasible, although it required a longer reaction time (entries 13 4 0.26 N/A 1000 94 98
2123). Using Takasagos borane-stabilized catalyst Ru- 14 4 0.13 N/A 500 59 62
MACHO-BH (4), similar yields were achieved with a 1 h 15 4 0.13 N/A 750 65 71
reaction time (entries 24 and 25). The extended reaction time 16 4 0.13 N/A 1000 77 82
is likely due to the required thermal dissociation of BH3 to form 17c 7 0.26 N/A 750 25 25
the active catalyst in situ. This could be visually observed while 18c,d 7 0.26 N/A 750 37 40
the reaction was run by monitoring the increase in reactor a
The reaction mixture contained 10 wt % MeOH relative to the
pressure with heating, followed by the consumption of the weight of CE-1270. bThe reaction mixture contained 20 wt % MeOH
hydrogen (pressure decrease) during the reaction. When Ru- relative to the weight of CE-1270. cReported in ref 18. dThe reaction
MACHO catalyst 3 was used, the pressure was built up was carried out at 115 C.
followed by a rapid decrease. With Ru-MACHO-BH catalyst 4,
the same pressure buildup was observed but the subsequent alcohols after 1 h and 91% after 3 h (entry 4). Reducing the
consumption of H2 typically required 1015 min to be visible. catalyst loading to 0.07 mol % at 500 psig resulted in a 92%
Recent computational studies on the analogous iron catalyst 7 yield after 1 h and 98% after 3 h (entry 8), thus giving a
conrm that the catalysis is initiated by BH3 dissociation.17,22 turnover number (TON) of 1400 for ester to alcohol
Two of the Gusev catalysts were evaluated under our conversion.23 Unfortunately, further reduction to 0.03 mol %
reaction conditions. It was found that catalyst 5 showed good catalyst loading only yielded 11% of the desired alcohols even
activity with >96% of the desired alcohols formed after 3 h at 1000 psig (entry 9).
(entries 26 and 27). The use of 6 necessitated the use of some The impact of including MeOH as a reaction solvent was
cosolvent (in our case THF) to achieve high yield. Without the examined next. When 10 wt % of MeOH relative to the starting
added solvent, 79% desired alcohols were obtained after 24 h esters was added, a 98% yield of alcohols was obtained after 3 h
(entry 28). In contrast, when THF was added, 96% yield was (Table 2, entry 10). A similar yield was obtained with 20 wt %
achieved after only 3 h (entry 29). For comparison purposes, of MeOH (entry 11). These experiments lead us to believe that
our previously reported data on the hydrogenation of CE-1270 there is no benet under these conditions with added solvent,
catalyzed by iron complex 7 were also tabulated here (entries nor is there a deleterious eect.
30 and 31). The catalytic activity of 7 is comparable to that of Use of the borane-stabilized catalyst 4 showed somewhat
Ru-MACHO-BH catalyst 4, suggesting that ruthenium-based diminished yields at the lower catalyst loadings. For example,
ester hydrogenation catalysts could be potentially replaced by 1000 psig was required with 0.26 mol % of catalyst to yield
their iron analogues. alcohols in 98% after 3 h (Table 2, entries 12 and 13). Further
Hydrogenation of CE-1270 on the 100 Gram Scale. reduction of the catalyst loading to 0.13 mol % yielded only
With small-scale conditions established, we wanted to test if the 82% of the alcohols after 3 h (entries 1416). Our previously
process was scalable using Takasagos catalysts 3 and 4. The reported iron catalyst 7 exhibited even lower activity (entry 17),
Milstein and Gusev catalysts were not chosen, due to cost and perhaps because it is more sensitive to impurities from the
availability issues. Moving to a 300 mL Parr reactor with 100 substrate. In addition, the slightly higher yield at a lower
g of CE-1270 also allowed for more convenient sampling temperature (115 C) suggested that this catalyst or catalytic
during the course of the reaction while ensuring better mixing species produced during the reaction is thermally unstable.
of the reactants. Starting with half of the previous catalyst Hydrogenation of CE-1270 on the Kilogram Scale. We
loading (0.55 mol % catalyst 3), 98% yield was obtained after 1 next moved to running reactions in a 1 gal Parr reactor. Using
h into a 3 h experiment (entry 1, Table 2)once again with no catalyst 3 (0.1 mol %), 98% of the desired alcohols was formed
exogenous solvent added. Subsequent reactions were run for 3 after 3 h at 135 C under 500 psig of H2 pressure. Reducing the
h with samples taken after 1 and 3 h. Further reduction of the catalyst loading to 0.05 mol % gave a 93% yield after 3 h with a
catalyst loading to 0.27 mol % resulted in no decrease in yield TON of 1860. Encouraged by these results, we needed to
after either 1 or 3 h (entry 2). Reducing the reaction pressure ensure that spent catalyst could be readily removed from the
to 500 psig was also tolerated within the limits of detection alcohol products by standard purication methods such as
(entry 3), though further reduction to 250 psig resulted in 77% distillation. ICP analysis on the crude reaction mixture showed
337 dx.doi.org/10.1021/om5011337 | Organometallics 2015, 34, 335339
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>1000 ppm of Ru and 751 ppm of P. Analysis of the alcohols
after distillation showed <1 ppm of Ru and <25 ppm of P,
conrming that the catalyst can be readily removed from the
product. No eorts have been made at this time to see if the
distillation residues can be reused in subsequent hydro-
genations as a way of recycling the catalyst.
conditions that are much more energy ecient than what the
current CuCr based processes would require. We have also
shown that catalysts which do not require an added base are
capable of promoting direct hydrogenation of the natural oils to
fatty alcohols. This methodology can potentially avoid the need
to make methyl ester in the future.

Hydrogenation of Coconut Oil. Moving beyond the
standard methyl ester to alcohol hydrogenation, we investigated EXPERIMENTAL SECTION
the direct hydrogenation of coconut oil to the desired fatty Materials. Fatty acid methyl esters (i.e., CE-1295 and CE-1270)
alcohols using homogeneous catalysts. This is currently not a and RBD (rened, bleached, and deodorized) coconut oil used in this
practical option using a copper chromite catalyst for a number study were manufactured by P&G Chemicals (http://www.
of reasons, primarily the negative impact of glycerides on the pgchemicals.com). Milstein catalysts 1 and 2 were purchased from
CuCr catalysts and the diculties in processing due to such Strem Chemicals. The Ru-MACHO catalyst 3 and Ru-MACHO-BH
issues as emulsion formation. Prior to our study, only osmium- catalyst 4 were purchased from either Strem Chemicals (for small
based catalysts had been used to hydrogenate natural oils, quantities) or Takasago (for large quantities). The Ru PNN-pincer
although these reactions were performed in toluene.12a,c Our catalyst 5 and Ru SNS-pincer catalyst 6 were purchased from Green
initial experiments were conducted in a 22 mL screw-cap Parr Centre Canada. The iron catalyst 7 was synthesized on the basis of a
procedure that was reported previously.18
reactor with the catalyst added on the basis of weight percent Hydrogenation of CE-1295 in a 22 mL Screw-Cap Parr
relative to the oilonce again, the reactions were run under Reactor. CE-1295 (1.61.7 g), catalyst, and NaOMe (at least 2 equiv
neat conditions. Starting with the Milstein catalyst 1 at 135 C based on moles of catalyst if required) were added to a 22 mL screw-
and 300 psig of H2 pressure, 21% of the desired alcohols was cap Parr reactor equipped with a magnetic stir bar. The reactor was
obtained after 24 h (entry 1, Table 3). Increasing the pressure closed, ushed with H2 four times, pressurized with H2, and placed in
an aluminum heating block that was preheated to the desired
Table 3. Catalytic Hydrogenation of Coconut Oil at 135 C temperature. After a designated period of time, the reactor was cooled
and opened and a sample was removed for GC analysis. Results of the
in a 22 mL Parr Reactor
representative experiments are summarized in Table 1.
cat. loading (wt pH2 time alcohol yieldb Hydrogenation of CE-1270 in a 300 mL Parr Reactor. As a
entry catalyst %) (psig) (h) (%) representative example, Ru-MACHO catalyst 3 (1.54 g, 2.54 mmol,
1 1 2.8 300 24 21 0.55 mol %), NaOMe (4.67 g of a 25 wt % solution in MeOH, 21.6
2 1 2.1 400 3 62
mmol, 8.5 equiv relative to 3), and CE-1270 (102 g, 461 mmol) were
added to the Parr reactor. The reactor was sealed, ushed with H2 four
3 1 2.4 400 24 62
times, and then pressurized to 750 psig. Stirring was set at 1000 rpm,
4 1 2.7 750 6 91 and the reaction mixture was quickly warmed to 135 C. The timing
5a 2 2.5 400 25 11 started when the temperature reached 135 C. The reaction was
6 4 2.6 750 6 2 continued at 135 C under 750 psig of H2 for 3 h with samples
7 4 2.6 750 22 76 removed (at time 0 min, 20 min, 40 min, 1 h, 2 h, and 3 h) for GC
8 4 2.8 750 24 84 analysis. At the end of the reaction, the reactor was cooled to room
9 7 2.0 750 23 12 temperature. For each sample, the combined GC yield for fatty
a
2.5 equiv of NaOMe was used relative to the catalyst. bCombined GC alcohols were determined with results summarized in Table 2.
Hydrogenation of CE-1270 in a 1 gal Parr Reactor. Ru-
yield for the fatty alcohols.
MACHO catalyst 3 (4.4 g, 0.0072 mol, 0.1 mol %), NaOMe (15.5 g of
a 25 wt % solution in MeOH, 0.072 mol, 10 equiv relative to 3), and
to 400 psig gave a dramatic increase in the yield to 62% after 3 CE-1270 (1.51 kg, 6.82 mol) were added to the Parr reactor. The
h (entry 2); however, no further increase was seen when the reactor was sealed, ushed with H2 four times, and then pressurized to
500 psig. Stirring was set at 600 rpm, and the reaction mixture was
reaction was run for 24 h (entry 3). A further increase in the H2 quickly warmed to 135 C. The timing started when the temperature
pressure to 750 psig yielded 91% of the desired alcohols after 6 reached 135 C. The reaction was continued at 135 C under 500 psig
h (entry 4). The use of the Milstein catalyst precursor 2 in of H2 for 4 h with samples removed (at time 0 min, 30 min, 1 h, 2 h, 3
conjunction with NaOMe gave only 11% of the alcohols after h, and 4 h) for GC analysis. At the end of the reaction, the reactor was
25 h (entry 5). This is likely due to the consumption of the cooled to room temperature.
added NaOMe as the transesterication reagent rather than Distillation of Fatty Alcohols To Remove Catalyst. Crude
removal of the chloride from 2. No further studies were alcohols from the homogeneous hydrogenation of CE-1270 using Ru-
conducted with either 2 or Ru-MACHO catalyst 3, which also MACHO catalyst 3 were ltered through a 0.2 m lter to remove any
requires the addition of a base such as NaOMe. Using the solids prior to distillation. Using a 10 in. tall, 1 in. Vigreux column, the
alcohols were distilled at 5 Torr to a nal pot temperature of 144 C.
borane-stabilized Ru-MACHO-BH catalyst 4, a yield of 84% Samples of the starting material and nal distilled alcohols were
alcohols was obtained after 24 h at 135 C under 750 psig of H2 submitted for ICP analysis (Ru detection limit of 1 ppm and P
pressure (entries 68). Unfortunately, the hydrogenation detection limit of 25 ppm).
reaction with the iron catalyst 7 was much less eective, Hydrogenation of RBD Coconut Oil in a 300 mL Parr
providing fatty alcohols in 12% yield after 23 h (entry 9). Reactor. As a representative example, Ru-MACHO-BH catalyst 4

CONCLUSIONS
In summary, we have described a high-yielding process using
commercially available homogeneous hydrogenation catalysts
for the reduction of methyl esters that we envision to be both
practical and scalable. Notable features include the running of
reactions without adding an exogenous solvent and utilizing
(1.11 g, 0.74 wt %) and RBD coconut oil (150 g) were added to the
Parr reactor. The reactor was sealed, ushed with H2 four times, and
then pressurized to 750 psig. Stirring was set at 1000 rpm, and the
reaction mixture was quickly warmed to 135 C. The timing started
when the temperature reached 135 C. The reaction was continued at
135 C under 750 psig of H2 for 24 h with samples removed (at time 0
min, 2 h, 4 h, 6 h, 8 h, and 24 h) for GC analysis. At the end of the
reaction, the reactor was cooled to room temperature. For each

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Organometallics Article

sample, the combined GC yield for fatty alcohols were determined (14) (a) Liu, C.; Xie, J.-H.; Li, Y.-L.; Chen, J.-Q.; Zhou, Q.-L. Angew.
with results summarized in Table 3. Chem., Int. Ed. 2013, 52, 593596. (b) Li, W.; Xie, J.-H.; Yuan, M.-L.;

Zhou, Q.-L. Green Chem. 2014, 16, 40814085.

(15) (a) Kuriyama, W.; Ino, Y.; Ogata, O.; Sayo, N.; Saito, T. Adv.
AUTHOR INFORMATION
Synth. Catal. 2010, 352, 9296. (b) Ino, Y.; Kuriyama, W.; Ogata, O.;
Corresponding Authors Matsumoto, T. Top. Catal. 2010, 53, 10191024. (c) Kuriyama, W.;
*E-mail for N.T.F.: fairweather.nt@pg.com. Matsumoto, T.; Ogata, O.; Ino, Y.; Aoki, K.; Tanaka, S.; Ishida, K.;
*E-mail for H.G.: hairong.guan@uc.edu. Kobayashi, T.; Sayo, N.; Saito, T. Org. Process Res. Dev. 2012, 16, 166
171.
Notes (16) Zell, T.; Ben-David, Y.; Milstein, D. Angew. Chem., Int. Ed. 2014,
The authors declare the following competing nancial 53, 46854689.
interest(s): portions of this work have been disclosed in a (17) Werkmeister, S.; Junge, K.; Wendt, B.; Alberico, E.; Jiao, H.;
provisional patent application with a serial number of 61/ Baumann, W.; Junge, H.; Gallou, F.; Beller, M. Angew. Chem., Int. Ed.
972927. 2014, 53, 87228726.

(18) Chakraborty, S.; Dai, H.; Bhattacharya, P.; Fairweather, N. T.;

Gibson, M. S.; Krause, J. A.; Guan, H. J. Am. Chem. Soc. 2014, 136,
ACKNOWLEDGMENTS 78697872.
(19) Only Takasagos Ru-MACHO catalyst 3 has been tested for a
We thank the Procter & Gamble Company and the Alfred P.
kilogram-scale synthesis of alcohols. For details, see ref 15c.
Sloan Foundation (research fellowship to H.G.) for support of (20) Other than our recently reported iron-catalyzed hydrogenation
this work. of FAMEs,18 there are only two known examples of hydrogenating an

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