Enantioselective Construction of Si-Stereogenic Center via Rhodium-Catalyzed Intermolecular Hydrosilylation of Alkene

Article abstract of DOI:10.1002/chem.202003506

Catalytic, enantioselective synthesis of stereogenic silicon compounds remains a challenge. Herein, we report a rhodium-catalyzed regio- and enantio-selective intermolecular hydrosilylation of alkene with prochiral dihydrosilane. This new method features a simple catalytic system, mild reaction conditions and a wide functional group tolerance.

Full text of DOI:10.1002/chem.202003506

Accepted Article
Accepted Article
Title: Enantioselective Construction of Si-Stereogenic Center via
Rhodium-Catalyzed Intermolecular Hydrosilylation of Alkene
Authors: Wei He, Tao He, Li-Chuan Liu, Wen-Peng Ma, Bin Li, and
Qing-Wei Zhang
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To be cited as: Chem. Eur. J. 10.1002/chem.202003506
Link to VoR: https://doi.org/10.1002/chem.202003506
01/2020

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Enantioselective Construction of Si-Stereogenic Center via
Rhodium-Catalyzed Intermolecular Hydrosilylation of Alkene
Tao He,[a] Li-Chuan Liu,[a] Wen-Peng Ma,[a] Bin Li,[a] Qing-Wei Zhang,*[b] and Wei He*[a]
[a]
T. He, L.-C. Liu, W.-P Ma, B Li, Prof. Dr. W. He
School of Pharmaceutical Sciences and MOE Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology Tsinghua University
Beijing, 100084 (P. R. China)
E-mail: whe@tsinghua.edu.cn
[b]
Prof. Dr. Q.-W. Zhang
Department of Chemistry, University of Science and Technology of China
Hefei, 230026 (P. R. China)
E-mail:qingweiz@ustc.edu.cn
Supporting information for this article is given via a link at the end of the document.
Abstract: Catalytic, enantioselective synthesis of stereogenic silicon
compound remains a grand challenge. Herein, we report a rhodium-
catalyzed regio- and enantio-selective intermolecular hydrosilylation
of alkene with prochiral dihydrosilane. This new method features a
simple catalytic system, mild reaction conditions and a wide functional
group tolerance.
developed a platinum-catalyzed intermolecular hydrosilylation of
internal alkynes[20] (Scheme 1b, top). In 2018, Huang and co-
workers achieved
a regio- and enantio-selective alkyne
hydrosilylation using Co complex and PyBox ligands (Scheme 1b,
middle).[21] In the same year, Hou and co-workers reported the
first stereo- and enantio- selective intermolecular alkene
hydrosilylation catalyzed by Scandium (Scheme 1b, bottom).[22]
Besides, diastereoselective hydrosilylation of alkynes also
emerged as one option for Si stereocenters construction.[24]
Despite of these important progresses, several problems remain
unsolved: (1) Functional group tolerance has not been fully
demonstrated. For example, substrates with hetero atoms such
as Br, I, B and so on are not shown to be viable. But these
synthetic handles are known to be highly desirable; (2) the
reported catalyst systems are tailor designed and the reactions
often require stringent conditions such as high temperature.
Stereogenic silicon compounds are of great importance in
medicinal chemistry[1] and material science.[2] The development of
enantioselective synthetic methods for these compounds is a
long-sought topic, but has been riddled with many challenges. A
major obstacle stems from the low stability of sp2-hybridized
silicon,[3] which defies the notion to access Si stereocenters via
asymmetric addition reactions that are routinely used on sp2-
hybridized carbon species. The classic methods to prepare
stereogenic silicon compounds often call for stoichiometric
amounts of chiral reagents.[4] While these methods are successful
and often reliable, the catalytic variants are more desirable in the
benefit of maximizing efficiency and minimizing waste production.
Among the catalytic methods, desymmetrization of prochiral
tetraorganosilanes (Si-C bonds) and dihydrosilanes (Si-H bonds)
represents the forefronts of stereogenic silicon chemistry.[5] In
terms of Si-C bond desymmetrization, Shintani’s group[6] and
others have made great progresses, including Si-C activation of
silacyclobutanes[6a,6b,7] stereoselective C-H bond activation,[8]
stereoselective
benzoylation
of
2-sila-1,3-propanediol,[9]
stereoselective diborylation of ethynylsilanes[10] and protoboration
of vinylsilanes.[11] Desymmetrization of Si-H bonds found an even
larger arena. One reason is that the resulting chiral
monohydrosilanes[5] are flexible and important synthetic
intermediates towards stereogenic silicons. The other reason is
that the higher reactivity of Si-H bonds allows them to react with
a broad range of partners. Among them are σ bonds including
inactivated C-H bonds[12](dehydrogenative couplings), O-H
bonds[13] (alcoholysis), Ar-X bonds[2b,14] (cross-coupling) and
carbenes.[15] Si-H reacting with π bonds (hydrosilylation)[16] has
long been exploited in a racemic manner, such as in the silicone
industry. The asymmetric variant can be dated as early as to 1974,
when Kumada[17] and Corriu[18] independently reported a stereo-
and enantio-selective ketone hydrosilylation. In 1994, as high as
>99% ee was achieved by employing (R)-Cy-Binap as the chiral
ligand (Scheme 1a) in this context.[19]
Catalytic, asymmetric desymmetrization of diyhdrosilanes with
carbon-carbon π bonds emerged much later. In 2012, Tomooka
1
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Scheme 1. Desymmetrization of prochiral secondary silanes via
enantioselective intermolecular hydrosilylation of un-saturated bonds.
14
(R)-L3
(R)-L3
(R)-L3
(R)-L3
(R)-L3
(R)-L3
RT
RT
RT
RT
RT
RT
DCE
68
73
65
32
79
86
67
68
66
65
70
70
15
Dioxane
MeOH
MeCN
THF
16
17
18[e]
19[f]
With our longstanding interest in Rh-catalyzed silicon chemistry,
we envisaged that commercially available Rh/chiral ligand system
might remedy the above-mentioned problems, as Rh is known to
have a better functional group tolerance. Ironically, Rh has
seldom been employed[24] as the catalyst for intermolecular
hydrosilylation of alkene, presumably due to regioselectivity
issue.[25] Herein, we report the development of Rh-catalyzed,
regio- and enantio-selective constructions of Si-stereogenic
centers via intermolecular hydrosilylation of alkenes from
prochiral hydrosilanes.
THF
[a] Reaction conditions: alkene 1b (0.1 mmol), dihydrosilane 2a (0.12 mmol, 1.2
equiv.), [Rh(cod)Cl]2 (2.0 μmol, 2% mol) and ligand (5.0 μmol, 5% mol) in
anhydrous THF (0.5 mL) at corresponding temperature for 4 h. [b] NMR yield
using mesitylene as internal standard. [c] Determined by chiral HPLC analysis.
[d] (R)-L1 = (R)-BINAP. [e] Using 1.0 equiv. of dihydrosilane. [f] Using 2.0 equiv.
of dihydrosilane.
We commenced our study with 1-(allyloxy)-4-methylbenzene 1b
and (2,6-dichlorophenyl)(methyl)silane 2a as the model
substrates (Table 1). Firstly, under the catalysis of [Rh(cod)Cl]2 (2
mol%) and (R)-BINAP (L1) (5 mol%) for 4 h at room temperature,
the anti-Markovnikov addition product 3ba was observed in a high
yield and a ee of 66% (entry 1). Following this result, a panel of
ligand then were screened. Ligand with narrower bite angles such
as (R)-MeO-Biphep (L2) gave a similar ee (entry 2). Bulkier (R)-
MeO-DM-Biphep (L3) gave a higher ee of 71% (entry 3). Ligand
with an increased stereo hindrance such as (R)-MeO-DTBM-
Biphep (L4) decreased the ee (entry 4). Electron-deficient (R)-
MeO-DCFM-Biphep (L5) only afforded a moderate ee (entry 5).
Similar results were obtained with Segphos-type ligands such as
(R)-Segphos (L6) (entry 6), (R)-DM-Segphos (L7) (entry 7), (R)-
DTBM-Segphos (L8) (entry 8). Without any ligand, a 20% yield of
3ba was observed, indicating a pronounced back ground reaction
(entry 9). Finally, we focused on (R)-MeO-DM-Biphep (L3) and
screened the reaction parameters. When the reaction was
conducted at 0 oC, the ee decreased to 54%, which was different
from Tomooka’s report in 2012[20] (entry 10). The reaction was
also conducted at 60 oC and a comparable ee was observed
(entry 11). The solvent was seen to play an important role. Low
polarity solvents such as toluene (entry 12) and n-hexane (entry
13) gave high yields and good stereoselectivity. In polar solvents
such as DCE (entry 14), dioxane (entry 15), MeOH (entry 16) and
MeCN (entry 17), both the reaction yield and ee decreased. It was
interesting that even in methanol, the hydrosilyation prevailed
over the alcoholysis.[13a] The stoichiometry of dihydrosilane was
shown to have little influence on the stereoselectivity (entries 18
and 19).
Table 1. Reaction conditions optimization.[a]
Entry
1
Ligand
(R)-L1[d]
(R)-L2
(R)-L3
(R)-L4
(R)-L5
(R)-L6
(R)-L7
(R)-L8
none
T (oC)
RT
RT
RT
RT
RT
RT
RT
RT
RT
0
Solvent
THF
Yield[b]
85
ee(%)[c]
66
67
71
30
58
68
70
24
-
2
THF
88
3
THF
84
4
THF
44
5
THF
80
6
THF
86
7
THF
84
8
THF
47
9
THF
20
10
11
12
13
(R)-L3
(R)-L3
(R)-L3
(R)-L3
THF
66
54
70
71
70
60
THF
80
RT
RT
Toluene
Hexane
83
92
Table 2. Substrates scope exploration with allylic ethers.[a,b,c]
2
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[a] Reaction conditions: alkene 1 (0.10 mmol, 1.0 equiv.), dihydrosilane 2a (0.12 mmol, 1.2 equiv.) and rhodium catalyst (2.0 μmol, 2 mol%) and MeO-DM-Biphep
(R)-L3 (5.0 μmol, 5 mol%) in anhydrous THF (0.5 mL) at room temperature for 4 h. [b] Isolated yield. [c] ee determined by HPLC analysis. [d] Performed on 3.0
mmol (0.49 g) scale. [e] Dihydrosilane 2a (0.24 mmol, 2.4 equiv.) was used. [f] Diastereomeric excess determined by HPLC analysis.
We demonstrate the reaction scope using the optimized reaction
conditions (Table 2). Unless noted otherwise, the regioselectivity
ratios for every substrates were greater than 20:1, favouring the
anti-Markovnikov products. The substituents on aryl with
different electronic demands were tested, as compared with
primary phenyl (3aa). Electron-donating groups such as para-
methyl (3ba), 3,5-dimethyl (3ca), para-tertiary butyl (3da), para-
methoxyl (3ea), ortho-methoxyl (3fa), methylenedioxy (3ga),
were generally tolerated. The reactions furnished the desired
products with high yields and good ee. The reaction could be
scaled up, such as in the case of 3.0 mmol reaction between
dihydrosilane 2a with alkene substrate 1e. Electron-withdrawing
groups such as para-trifluoromethyl (3ha) and para-ester (3ia)
lead to slightly decreased yields and stereoselectivity while
fluorine was an exception (3ja), which afforded a 88% yield and
an ee of 78%. Other halogen such as para-chlorine (3ka), para-
bromine (3la) and para-iodine (3ma) had little influence on the
yield or ee. The compatibility with halogen atoms especially
iodine would enable further elaboration of the product via cross-
coupling or carbon anion chemistry. The more conjugated 2-
naphthyl (3na), 1-naphthyl (3oa), para-phenyl (3pa) and ortho-
phenyl (3qa) also afford good yields and stereoselectivity. As B
and Si atoms have orthogonal reactivity to that of halogens, we
also incorporated them in the substrates (e.g. 3ra, 3sa). Both of
them are shown to be competent substrates in terms of yields
and ee. Good de (77%) were also afforded when meeting
symmetrical arylallylic ether (3ta), accompanied with high yield.
results were probably due to the stronger coordination ability of
nitrogen compared with oxygen.
Scheme 2. Exploration with allylic amine as substrate. Reaction conditions:
alkene 4 (0.10 mmol), dihydrosilane 2a (0.12 mmol, 1.2 equiv.), [Rh(cod)Cl]2
(2.0 μmol, 2 mol%) and MeO-DM-Biphep (R)-L3 (5.0 μmol, 5 mol%) in
anhydrous THF (0.5 mL) at room temperature for 4 h. Isolated yield. ee
determined by HPLC analysis.
Several reactions were conducted to investigate the steric effects
of dihydrosilanes (Scheme 3). With slightly bulkier ethyl rather
methyl, dihydrosilane 2b afforded a yield of 72% with diminished
ee of 59%. Changing the Cl into Me, as in the case of 2c, resulted
in a low yield and a low ee. Changing the Cl into Br as in the case
of 2d completely shut down the reaction. These results showed
that the steric environment around the Si atoms are essential for
both the reactivity of the Si-H bond and the enantioselectivity.
We also probed the reaction with allylic amine as substrate
(Scheme 2). Substrate N-allylphenylaniline gave a slightly higher
yield and ee (5aa) under than the ethers. Similar yield and ee
was observed with the N-allyl indoles (5ba). These slightly better
3
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Acknowledgements
We gratefully acknowledge financial support from the National
Natural Science Foundation of China (No. 21625104 and
21971133) and the National Key Research and Development
Program of China (2017YFA0505200).
Keywords: Desymmetrization • Hydrosilylation • Si-stereogenic
center • Rhodium • Alkene
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In summary, we have developed
a
Rh-catalyzed
enantioselective construction of Si-stereogenic center via
intermolecular hydrosilylation of alkene with prochiral
dihydrosilanes. The reaction affords a series of stereogenic
tertiary silanes in good yields and enantioselectivities. Compared
to known methods, the current method shows a better tolerance
of functional groups and uses a simple, commercially available
catalyst system. This work demonstrated that Rh should warrant
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4
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10.1002/chem.202003506
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COMMUNICATION
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5
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Entry for the Table of Contents
A rhodium-catalyzed regio- and stereoselective hydrosilylation
from prochiral dihydrosilane to terminal alkene is realized,
which extends the limited success of asymmetric construction
of Si-stereogenic centers. The new reaction features simple
reaction condition, a general substrate scope and excellent
functional group compatibility.
6
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