Catalytic synthesis of functional silicon-stereogenic silanes through Candida antarctica lipase B catalyzed remote desymmetrization of silicon-centered diols

Article abstract of DOI:10.1002/ejoc.201300932

A series of silicon-containing diols are synthesized and used in lipase-catalyzed remote desymmetrization. This synthetic method is valuable in the construction of optically active silicon-stereogenic organosilicon compounds. Good enantioselectivities of the remote desymmetrization was achieved with Candida antarctica lipase B (CAL-B (up to 90:10 er). Remote desymmetrization: A series of silicon-containing diols are synthesized and used in Candida antarctica lipase B (CAL-B)-catalyzed remote desymmetrization. This synthetic method is valuable in the construction of optically active silicon-stereogenic organosilicon compounds. Copyright

Full text of DOI:10.1002/ejoc.201300932

SHORT COMMUNICATION
DOI: 10.1002/ejoc.201300932
Catalytic Synthesis of Functional Silicon-Stereogenic Silanes through Candida
antarctica Lipase B Catalyzed Remote Desymmetrization of Silicon-Centered
Diols
Xing Lu,[a] Li Li,[a] Wei Yang,[a] Kezhi Jiang,[a] Ke-Fang Yang,[a] Zhan-Jiang Zheng,[a] and
Li-Wen Xu*[a,b]
Keywords: Asymmetric catalysis / Chirality / Silicon / Enzymes / Diols
A series of silicon-containing diols are synthesized and used
in lipase-catalyzed remote desymmetrization. This synthetic
method is valuable in the construction of optically active sili-
con-stereogenic organosilicon compounds. Good enantio-
selectivities of the remote desymmetrization was achieved
with Candida antarctica lipase B (CAL-B) (up to 90:10er).
the prostereogenic centers rely on the chemoselective trans-
formation of two symmetric reactive centers are particularly
challenging, as the catalyst must simultaneously mediate
bond formation and bond cleavage.[2b,6] Very recently, some
successful desymmetrization protocols for the synthesis of
silicon-stereogenic silanes catalyzed by transition-metal
complexes revealed the potential of asymmetric catalysis in
organosilicon chemistry.[2b,7] Considerable efforts have also
been made in the enantioselective enzymatic synthesis of
enantiomerically pure silicon-containing compounds
through lipase-catalyzed kinetic resolution and desymme-
trization.[8] Unfortunately, lipase-catalyzed kinetic resolu-
tion and desymmetrization of silicon-containing com-
pounds is not as easy as imagined. The only published solu-
tion to the lipase-catalyzed desymmetric synthesis of sili-
con-stereogenic silanes is the procedure reported by Blanco
and Djerourou, in which the monoester-containing silicon-
stereogenic silane was obtained with only moderate enan-
tiomeric excess.[8e] Despite the broad utility of enzymatic
approaches in asymmetric catalysis,[9] little attention has
been paid to remote desymmetrization of prochiral com-
pounds.[10] Interestingly, to the best of our knowledge, there
is no report on the remote desymmetrization of prochiral
silicon-centered diols that is catalyzed by either enzymes or
chiral metal-based catalysts.
Introduction
Organosilicon chemistry has had a broad impact on or-
ganic synthesis and asymmetric catalysis as a result of the
wide application of organosilicon compounds or silicon-
containing reagents in organic chemistry.[1] Among various
organosilicon compounds, chiral silanes and nonracemic
organosilicon compounds that possess sp3 central chirality
on the silicon atom are highly attractive and are potentially
useful chiral molecules.[2] Over the past decades, silicon-
stereogenic silanes have been important as chiral building
blocks and reagents in asymmetric catalysis, as the concept
of chirality transfer from silicon to carbon is recognized as
an efficient strategy in reagent-controlled reactions.[3] How-
ever, the synthesis and application of silicon-stereogenic
silanes remains a fundamental challenge in chiral organo-
silicon chemistry, as there is a deficit of natural chiral
silanes. Moreover, the construction of silicon-stereogenic
silanes, especially the catalytic synthesis of functional chiral
silanes, is still a challenge.
Although the synthesis of silicon-stereogenic silanes
through catalytic desymmetrization of dihydrosilanes was
reported almost 40 years ago,[4] limited progress was made
in the preparation of enantiomeric chiral silanes prior to
1994.[5] In particular, desymmetrization reactions in which
Notably, it is well known that remote asymmetric induc-
tion with high enantioselectivity is one of the most chal-
lenging problems in asymmetric synthesis, in that the same
and remote reactive site is generally difficult to be induced
stereoselectively by substrate-controlled catalyst.[11] Herein,
we decided to investigate the enzymatic remote desymme-
trization of prochiral silicon-containing diols bearing a re-
active hydroxy group distant from the prostereogenic silicon
atom by five bonds.
[a] Key Laboratory of Organosilicon Chemistry and Material
Technology of Ministry of Education, Hangzhou Normal
University,
Hangzhou, 310012, P. R. China
E-mail: liwenxu@hznu.edu.cn
Homepage: http://yjg.hznu.edu.cn/sysgk/xsdtr/308604.shtml
[b] State Key Laboratory for Oxo Synthesis and Selective
Oxidation, Lanzhou Institute of Chemical Physics, Chinese
Academy of Sciences,
Lanzhou, 730000, P. R. China
E-mail: licpxulw@yahoo.com
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201300932.
First, we focused on the straightforward preparation of
prochiral 3,3Ј-[methyl(phenyl)silanediyl]bis(3,1-phenylene)-
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Catalytic Synthesis of Functional Silicon-Stereogenic Silanes
dimethanol (1a), an ideal model substrate for the optimiza-
tion of the synthetic enzymatic study. Starting from com-
mercially available 3-bromobenzaldehyde, 1a was synthe-
sized easily in good yield (Supporting Information).[12] Sim-
ple molecular mechanics calculations underscored the par-
ticular challenge of the remote desymmetrization. As shown
in Figure 1, the reactive site of the alcohol is Ͼ6.6 Å from
the prochiral stereogenic silicon center of the molecule, and
the enantiotopic hydroxy group is at a distance of Ͼ1 nm
(12.367 Å between the two oxygen atoms).
Because of the excellent levels of stereoselectivity shown
by Candida antarctica lipase B (CAL-B), also currently
known as Novozym 435 (a commercially available form of
CAL-B), in the asymmetric kinetic resolution of
alcohols,[13] we decided to use the CAL-B-catalyzed system
for the remote desymmetrization of silicon-containing diol
1a. The initial approach to the remote desymmetrization of
1a was performed to examine the activity of CAL-B as well
as other lipases, such as lipozyme RM IM (from Rhizo-
Figure 1. Substrate metrics for silicon-based diol 1a: A defined dis-
tance of 6.615 Å between the desired reactive site (-OH) and the
prochiral stereogenic center (Si atom) and a distance of 12.367 Å
separates the enantiotopic hydroxy-containing methyl groups.
mucor miehei) and lipozyme TL IM (from Thermomyces erate yield and chemoselectivity for monoacetate 2a, but the
lanuginose). CAL-B (Table 1, entry 1) and TL IM (Table 1, enantiomeric excess of the desired product was not good
entry 2) showed excellent levels of catalytic activity and pro- (30%ee; Table 1, entry 3). Thus, we decided to further opti-
vided monoacetate 2a and diacetate 3a in good yields. In mize the desymmetrization reaction with CAL-B. Variation
the first case, monoacetate 2a was formed in 98% yield with of the acylation reagents resulted in different conversions
up to 78%ee. In the second case, the ratio of monoacetate and enantioselectivities (Table 1, entries 4–6). Both 4-
to diacetate (i.e., 2a/3a) was not high enough and the enan- chlorophenylacetate and vinyl acetate were found to be ef-
tiomeric excess was moderate (61%ee). Nevertheless, the fective as acylated reagents in terms of promising enantio-
use of commercially available lipozyme RM IM gave mod- selectivities (70 and 65%ee, respectively). The acetylation
Table 1. Enzymatic desymmetrization of silicon-containing diol 1a by using lipase.[a]
Entry
Enzyme
R
Solvent
Yield [%][b]
Ratio of 2a/3a[b]
ee of 2a [%][c]
1
2
3
4
5
6
7
8
CAL-B
TL IM
RM IM
CAL-B
CAL-B
CAL-B
CAL-B
CAL-B
CAL-B
CAL-B
CAL-B
CAL-B
CAL-B
CAL-B
CAL-B
CAL-B
CAL-B
CAL-B
CH3COO
CH3COO
CH3COO
Cl
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CH2Cl2
THF
Ͼ99
98
61
90
85
98:2
81:17
55:6
52:38
65:20
75:4
78[d]
61
30
0
p-ClPhO
CH2=CHO
CH3COO
CH3COO
CH3COO
CH3COO
CH3COO
CH3COO
CH3COO
CH3COO
CH3COO
CH3COO
CH3COO
CH3COO
70
65
38
41
79
Ͼ99
Ͼ99
trace[e]
Ͼ99
trace
trace
Ͼ99
74
90
78
Ͼ99
64
62:38
28:72
[f]
[f]
9
toluene
Et2O
–
–
10
11
12
13
14
15
16
17
18
26:73
–
11
–
–
DMSO
CH3OH
EtOAc
CH3CN
acetone
CH3NO2
CCl4
–
0:Ͼ99
65:9
55:35
77:2
95:5
55:9
–
0
–7[g]
0
51
0
1,4-dioxane
[a] Reaction conditions: 1a (0.5 mmol), enzyme (35 mg), acylation reagent (1.25 equiv.), CHCl3 (1 mL), r.t., 16 h. [b] The yield was mea-
sured by GC analysis. [c] Enantiomeric excess of 2a was determined by HPLC analysis on a chiral stationary phase (see Supporting
Information for details). [d] The isolated yield of 2a was 90%. [e] The reaction was slow and the conversion was very low (Ͻ10%). [f] The
ratio of 2a/3a and the enantiomeric excess of 2a were not determined. [g] A reversal in the enantioselectivity of 2a was found in acetone
relative to that found in other solvents.
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X. Lu, L. Li, W. Yang, K. Jiang, K.-F. Yang, Z.-J. Zheng, L.-W. Xu
SHORT COMMUNICATION
of prochiral diol 1a with acetyl chloride was not enantio- CCl4 were good solvents in terms of conversion (compar-
selective, but product 2a was obtained in good yield with able to that in chloroform), low to moderate enantio-
moderate chemoselectivity (2a/3a = 52:38; Table 1, entry 4). selectivities were obtained (11–51%ee). Notably, if EtOAc
Thus, the use of acetyl chloride as the acylating agent was was used as the solvent, only product 3a was obtained in
not suitable, because it is a chemical reaction and not an high yield (Table 1, entry 13). Interestingly, a reversal in the
enzymatic process.
enantioselectivity was observed if the reaction was per-
To find the best reaction conditions, other parameters formed in acetone (Table 1, entry 15). All of these results
that can have an influence on the enzymatic performance, suggested that the chiral environment of the enzyme (i.e.,
such as the loading of the lipase catalyst and temperature, CAL-B) could be changed by the solvent. Inspired by these
were investigated, and the effects of solvents and additives, results, various compounds with promising catalytic activi-
such as various metals and chiral amino acids, on the ties in organic synthesis, including chiral amino acids and
enantioselectivities were also evaluated. Unfortunately, no achiral transition-metal salts and complexes, were used in
increase in the enantioselectivity was achieved (Table 1, see catalytic amounts (10 mol-%) as additives in the CAL-B-
also Tables S1–S3, Supporting Information), as there was catalyzed remote desymmetrization of silicon-containing
no positive influence on the active site of CAL-B. For ex- diol 1a. Unfortunately, all of the additives evaluated in this
ample, the enantioselectivities obtained in the screened sol- work did not improve the enantioselectivity (Tables S2 and
vents were lower than that obtained in CHCl3 (Table 1, en- S3, Supporting Information).
tries 7–18; see also Table S1, Supporting Information). If
The optimized reaction conditions with CAL-B and ace-
toluene, DMSO, or MeOH was used as the solvent, only a tic anhydride were applied to the remote desymmetrization
trace amount of the desired product was detected (Table 1, of a number of silicon-containing prochiral diols. All of the
entries 9, 11, and 12). Reactions in 1,4-dioxane, CH3CN, results are summarized in Scheme 1. A wide range of sili-
and CH3NO2 gave the product in moderate to good yields, con-containing prochiral diols (i.e., 1a–q) could be used in
but the reaction was not enantioselective (Table 1, en- this remote desymmetrization reaction. The yield of the de-
tries 14, 16, and 18). Although CH2Cl2, THF, Et2O, and symmetrization reaction was not affected by either aryl or
Scheme 1. Synthesis of silicon-stereogenic silanes by remote desymmetrization of prochiral silicon-containing diols. Reaction conditions:
1 (0.125 mmol), CAL-B (8–10 mg), r.t., 14–16 h. The yields of 2a–q were determined after flash chromatography, and the enantiomeric
excess values of 2a–q were determined by HPLC on a chiral stationary phase.
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Catalytic Synthesis of Functional Silicon-Stereogenic Silanes
8000 PLUg–1), lipozyme RM IM (from Rhizomucor miehei, avail-
able immobilized on macroporous anion exchange resin, 5–
6 BAUNg–1), and lipozyme TL IM (from Thermomyces lanuginose,
available immobilized on silica gel, 250 IUNg–1), were supplied by
Novozymes China Headquarters (Beijing) and Gaoruisen Co.
(Beijing, China). IR spectra were recorded with a Bruker IR spec-
trometer. 1H NMR and 13C NMR were recorded at 400 and
100 MHz, respectively, and 29Si NMR spectra were recorded at
80 Hz with an Advance (Bruker) 400 MHz NMR spectrometer and
were referenced to the internal solvent signals (1H NMR: CDCl3
alkyl groups (18 examples, 68–93% isolated yield). A vari-
ety of reactive functional groups, such as vinyl and hydro-
gen (Si–H), survived under the reaction conditions.
Scheme 1 also illustrates that in reactions of silicon-contain-
ing prochiral diols with a phenyl or vinyl group (R1 = Ph
or CH=CH2; 1a, 1b, 1h, 1l, 1p, and 1q), the corresponding
silicon-stereogenic silanes were produced with good
enantioselectivities (61–78%ee). It is also interesting that
small substituents on the silicon atom led to low enantio-
selectivities (e.g., 2i–k), and better results were obtained at δ = 7.26 ppm. 13C NMR: CDCl3 at δ = 77.0 ppm, DMSO at δ
= 39.43 ppm) without tetramethylsilane as the internal standard.
Thin-layer chromatography was performed by using silica gel, F254
TLC plates and visualized with ultraviolet light. EI and CI mass
spectra were performed with a Trace DSQ GC–MS spectrometer.
The products were confirmed by GC–MS and HRMS and the us-
ual spectroscopy methods (1H NMR, 13C NMR, 29Si NMR). The
ESI-MS analysis of the samples was performed with an LCQ ad-
vantage mass spectrometer (ThermoFisher Company, USA)
equipped with an ESI ion source in the positive ionization mode
with data acquisition by using the Xcalibur software (version 1.4).
with larger aliphatic groups attached to the silicon center.
Furthermore, silicon-containing prochiral diols with a
3,3,3-trifluoropropyl group led to better enantioselectivity
(i.e., 2c and 2h, up to 80%ee). Thus, the structure–enantio-
selectivity profile for this CAL-B-catalyzed remote desym-
metrization is clearly dependent on the structures of the
substituted silicon-centered diols.[14] Notably, although the
remote desymmetrization reaction of diols with alkyl
groups for R1 and R2 afforded low levels of enantio-
selectivities, the reaction results provided the direct observa-
tion of an enzyme catalyst–substrate complex, in which
intermolecular interactions, including hydrogen bonding
and π–π stacking, between the silicon-stereogenic silane and
the active center of CAL-B[15] is definitively important for
selective interaction and stereoselective remote induction.
To determine the absolute configuration of silicon-
stereogenic silane 2, the calculated circular dichroism (CD)
General Procedure for the Enzymatic Desymmetrization of Silicon-
Containing Diols: To a solution of 1a (42 mg, 125 μmol) in CHCl3
(1.5 mL) at room temperature was added CAL-B (N-435, 8.0 mg)
followed by acetic anhydride (17.6 μL, 187.5 μmol). The solution
was then stirred overnight for 12–14 h and quenched by the ad-
dition of ether (1 mL). The mixture was diluted with water, and
EtOAc was added. The reaction solution was separated, and the
aqueous solution was extracted with EtOAc (2ϫ 5 mL). The com-
results were compared to the experimental results.[16] As a bined organic extract was dried with Na2SO4, filtered, and concen-
trated in vacuo. The residue was purified by flash chromatography
(25% EtOAc/hexanes) to afford monoacetate 2a as colorless oil,
90% yield. HPLC (Daicel Chiralcel OD-H column, hexane/2-prop-
anol = 95:5, flow = 1.0 mLmin–1): tR = 17.4 (minor enantio-
mer), 19.0 min (major enantiomer); 78%ee. [α]2D5 = +465.0 (c = 1.0,
CHCl3). 1H NMR (400 MHz, CDCl3): δ = 7.53–7.34 (m, 13 H),
5.08 (s, 2 H), 4.66 (s, 2 H), 2.07 (s, 3 H), 0.86 (s, 3 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 171.07, 140.33, 136.60, 136.24,
135.69, 135.19, 134.68, 133.77, 129.49, 128.41, 128.05, 66.48, 65.44,
21.03, –3.33 ppm. 29Si NMR (80 MHz): δ = –10.84 (s) ppm. IR
result of the structural similarities of 2a–p, we compared
the calculated CD spectra with the experimental spectra of
2a and 2l as representative examples (Figures S1–S4, Sup-
porting Information), which proved the (S) configuration
of the stereogenic silicon center.
Conclusions
In summary, a series of silicon-containing diols was de-
signed and prepared for the synthesis of chiral functional
silanes through an asymmetric chemoenzymatic transfor-
mation. The lipase-catalyzed remote desymmetrization
proved to be a valuable synthetic method for the construc-
tion of optically active silicon-stereogenic organosilicon
compounds (up to 90:10er). Notably, the results of the cata-
lytic remote desymmetrization of silicon-centered diols re-
vealed that a 3D enzyme–substrate complex might be
formed under the reaction conditions. Further modification
of this remote desymmetrization for the preparation of sili-
con-stereogenic silanes and clarification of the enzyme–sub-
strate interactions in the asymmetric CAL-B catalysis is on-
going in our laboratories.
(neat): ν = 3418.81, 3047.11, 3021.25, 2956.11, 1736.78, 1477.10,
˜
1427.87, 1410.65, 1375.97, 1359.50, 1225.89, 1175.40, 1112.04,
1082.36, 1025.37, 968.08, 923.22, 869.31, 775.72, 725.74, 699.73,
664.72, 618.32 cm–1. HRMS (ESI-TOF): calcd. for C23H24NaO3Si
[M + Na]+ 399.1387; found 399.1399.
All of the products were confirmed by GC–MS, NMR and IR
spectroscopy, and HRMS (see Supporting Information).
Supporting Information (see footnote on the first page of this arti-
cle): General remarks; NMR, IR, and other useful spectroscopic
data for 1 and 2; details of the HPLC separation conditions; and
CD spectra.
Acknowledgments
Financial support by the National Natural Science Foundation of
China (NSFC) (grant numbers 21173064 and 21205025), Zhejiang
Provincial Natural Science Foundation of China (ZPNSFC)
(Q12B020037), and the Program for Excellent Young Teachers in
Experimental Section
General Methods: All reagents and solvents were used directly with-
out purification. Flash column chromatography was performed
with silica (200–300 mesh). Candida antarctica lipase B (CAL-B, Hangzhou Normal University (HNUEYT) (JTAS 2011-01-014) is
available immobilized on polyacrylamide as Novozyme-435, appreciated.
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SHORT COMMUNICATION
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Received: June 24, 2013
Published Online: August 8, 2013
Eur. J. Org. Chem. 2013, 5814–5819
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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