10.1002/anie.202009912
Angewandte Chemie International Edition
RESEARCH ARTICLE
stable in the reaction systems, the one-pot trap of them with
Keywords: asymmetric catalysis • silicon-stereogenic silanes •
chiral dihydrobenzosiloles • enantioselective C(sp3)–H silylation •
stereospecific hydrosilylation
alkenes in
a stereospecific fashion stabilized the silicon-
stereogenic center, providing an elegant strategy for the
construction of various asymmetrically tetrasubstituted
dihydrobenzosiloles.[10] This process also suggests that the
intramolecular C(sp3)−H silylation is more favoured than the
intermolecular alkene hydrosilylation. In addition, we believe that
the alkene could also play a role as the hydrogen acceptor in the
first dehydrogenative cyclization. For example, we could isolate
the hydrogenated product 1-ethyl-4-methoxybenzene in 81%
yield when 1-methoxy-4-vinylbenzene was used in the reaction
(Table 2, 3u). Further detailed mechanistic studies are in
progress, which will be disclosed in due course.
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Conclusion
In summary, we develop an enantioselective aliphatic C–H
silylation/alkene hydrosilylation methodology for the efficient
synthesis of silicon-stereogenic dihydrobenzosiloles. This
[3]
process involves
a
highly selective asymmetric C(sp3)–H
silylation of dihydrosilanes, followed by a stereospecific alkene
hydrosilylation. A wide range of dihydrosilanes and alkenes
displaying various functional groups are compatible with this
process, giving access to a variety of highly functionalized
silicon-stereogenic dihydrobenzosiloles in good to excellent
yields and enantioselectivities. We believe that the operational
simplicity and efficacy of this enantioselective C(sp3)–H silylation
and broad scope of the asymmetrically tetrasubstituted silanes
displaying functional diversity will find widespread use among
synthetic chemistry, medicinal chemistry, and materials science.
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Experimental Section
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Inside an argon-filled glovebox, an oven-dried 5 mL microwave reaction
tube was charged with [Rh(cod)Cl]2 (1 mg, 0.002 mmol), (R, Sp)-
Josiphos (2.2 mg, 0.004 mmol) and anhydrous DCE (1 mL). After being
stirred at room temperature for 5-10 min, dihydrosilane (0.10 mmol) and
alkene (0.22 mmol) were added. The tube was capped and taken outside
of the glovebox. The resulting mixture was placed into a pre-heated (100
oC) aluminium block and stirred for 1 hour. Then the reaction mixture was
diluted with dichloromethane (2 mL) and filtered through a plug of silica
gel, which was rinsed with petroleum/ ether acetate. The filtrate was
concentrated and then purified by preparative TCL to afford target
product. The enantiomeric excess was determined by chiral HPLC
analysis. Corresponding racemic samples were obtained as references
by carrying out the reactions at the identical conditions with (±)-BINAP or
(±)-Josiphos.
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Acknowledgements
We are grateful for financial support from the National Natural
Science Foundation of China (21901104), the Thousand Talents
Program for Young Scholars, the start-up fund from Southern
University of Science and Technology, the Shenzhen Nobel
Prize Scientists Laboratory Project (C17783101), and
Guangdong Provincial Key Laboratory of Catalysis (No.
2020B121201002). We also thank Dr. Xiao-Yong Chang for
assistance in solving the X-ray structures.
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