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. 2023 Feb 9;8(7):6854-6859.
doi: 10.1021/acsomega.2c07581. eCollection 2023 Feb 21.

Stereo- and Regiospecific SN2' Reaction of MBH Adducts with Isocyanoacetates: en Route to Transition-Metal-Free α-Allylation of Isocyanoacetates

Chunsong Xie  1   2 , Song Wu  2 , Runmei Zhang  2
Affiliations

Stereo- and Regiospecific SN2' Reaction of MBH Adducts with Isocyanoacetates: en Route to Transition-Metal-Free α-Allylation of Isocyanoacetates

Chunsong Xie et al. ACS Omega. .

Abstract

Herein, we report that under mild and transition-metal-free conditions an unprecedented and practical SN2' reaction of Morita-Baylis-Hillman adducts with isocyanoacetates takes place in a stereo- and regiospecific manner. This reaction which tolerates a wide variety of functionalities delivers transformable α-allylated isocyanoacetates in high efficiencies. Preliminary studies on the asymmetric version of this reaction indicate that ZnEt2/chiral amino alcohol combinations are an asymmetric catalytic system for this transformation, giving an enantioenriched α-allylated isocyanoacetate with a chiral quaternary carbon in a high yield.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. α-Allylation of Isocyanoacetates
Scheme 2
Scheme 2. Proposed Mechanism of the Reaction
Scheme 3
Scheme 3. Post-Transformations
Scheme 4
Scheme 4. Asymmetric Version of the Transformation
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