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. 2010 Jan 1;34(7):1309-1316.
doi: 10.1039/c0nj00063a.

A Stereoselective Intramolecular Cyclopropanation via a De Novo Class of Push-Pull Carbenes Derived from DMDO-Epoxidations of Chiral Ynamides

Hongyan Li  1 , Jennifer E Antoline, Jin-Haek Yang, Ziyad F Al-Rashid, Richard P Hsung
Affiliations

A Stereoselective Intramolecular Cyclopropanation via a De Novo Class of Push-Pull Carbenes Derived from DMDO-Epoxidations of Chiral Ynamides

Hongyan Li et al. New J Chem. .

Abstract

This work describes the first examples of diastereoselective intramolecular cyclopropanations of a de novo class of push-pull carbenes derived from DMDO-epoxidations of chiral ynamides. This reaction sequence essentially constitutes a tandem epoxidation-cyclopropanation that effectively gives arise to a series of structurally unique amido-cyclopropanes. A plausible mechanistic model is proposed revealing insights into this novel cyclopropanation process.

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Figures

Figure
Figure
A Proposed Mechanistic Model
Scheme 1
Scheme 1
De Nov Carbenes from Epoxidations of Ynamides.
Scheme 2
Scheme 2
Synthesis of Ynamide 11.
Scheme 3
Scheme 3
Epoxidation and Cyclopropanation of Ynamides 11 and 13.
Scheme 4
Scheme 4
A Proposed Mechanistic Model.
Scheme 5
Scheme 5
Ynamide-Epoxidation–Cyclopropanation Examples.
Scheme 6
Scheme 6
Attempts of Improving the Diastereoselectivity.
Scheme 7
Scheme 7
Epoxidation–Cyclopropanations of Ynamides 27–29.
See this image and copyright information in PMC

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