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. 2023 Mar 28;14(17):4641-4646.
doi: 10.1039/d2sc06349b. eCollection 2023 May 3.

Chiral spirosiladiphosphines: ligand development and applications in Rh-catalyzed asymmetric hydrosilylation/cyclization of 1,6-enynes with enhanced reactivity

Fei Hou  1   2 , Minjie Liu  1   2 , Tong Ru  1   2 , Zequn Tan  1   2 , Yingtang Ning  1   2 , Fen-Er Chen  1   2
Affiliations

Chiral spirosiladiphosphines: ligand development and applications in Rh-catalyzed asymmetric hydrosilylation/cyclization of 1,6-enynes with enhanced reactivity

Fei Hou et al. Chem Sci. .

Abstract

Spirodiphosphines have been successfully applied in various asymmetric catalytic transformations. However, controlling the coordinating conformations by the direct displacement of the spiro atom remains elusive. Herein, we report the application of Si-centered spirodiphosphine (Si-SDP) ligands in the enantioselective hydrosilylation/cyclization of 1,6-enynes. The Si-SDPs showed superior reactivity to existing C2-symmetric diphosphines, allowing the generation of a range of chiral pyrrolidines with high yields and enantioselectivity (up to 96% yield and 92% ee) at room temperature with low catalyst loading. The mechanistic observations were consistent with the modified Chalk-Harrod mechanism, and the high reactivity of Si-SDPs was further leveraged for the room-temperature Rh-catalyzed hydrosilylation of alkynes.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. Examples of C2-symmetric diphosphines.
Scheme 1
Scheme 1. Rh-catalyzed hydrosilylation/cyclization.
Scheme 2
Scheme 2. Scope of Rh-L3 catalyzed silylcyclization a–c.a Reactions were performed with 1a (0.2 mmol), 2a (0.4 mmol), Rh(cod)2BF4 (1.5 mol%), and L3 (3 mol%) in DCE (2.0 mL).b Yields of isolated 3.c ee values were determined by chiral HPLC of the desilylated compounds.
Scheme 3
Scheme 3. Mechanistic insights into Rh-L3 catalyzed silylcyclization.
Scheme 4
Scheme 4. Room-temperature hydrosilylation of alkynes.
See this image and copyright information in PMC

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