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. 2011 Sep 16;13(18):4870-2.
doi: 10.1021/ol201949h. Epub 2011 Aug 18.

Reactivity of N-(1,2,4-triazolyl)-substituted 1,2,3-triazoles

Mikhail Zibinsky  1 , Valery V Fokin
Affiliations

Reactivity of N-(1,2,4-triazolyl)-substituted 1,2,3-triazoles

Mikhail Zibinsky et al. Org Lett. .

Abstract

Synthetically useful rhodium(II) carbenes were obtained from N-(1,2,4-triazolyl)-substituted 1,2,3-triazoles and Rh(II) carboxylates. The electron-withdrawing 1,2,4-triazolyl group reveals the heretofore unknown reactivity of nonsulfonyl 1,2,3-triazoles, which exhibit the reactivity of diazo compounds. The resulting carbenes provide ready asymmetric access to secondary homoaminocyclopropanes (80-95% ee, dr >20:1) via reactions with olefins and also engage in efficient transannulation reactions with nitriles.

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Figures

Scheme 1
Scheme 1. Azavinyl carbenes from 1,2,3-triazoles
Scheme 2
Scheme 2. Cyclopropanation of styrene with triazole 3a catalyzed by Rh(II) carboxylates
Scheme 3
Scheme 3. Rh2(S-NTTL)4–catalyzed enantio– and diastereoselective cyclopropanation of alkenes with triazoles 3
Scheme 4
Scheme 4. Rh2(esp)2 catalyzed transannulation of triazoles 3 with nitriles
Scheme 5
Scheme 5. Relative reactivity of 3a and N-sulfonyl triazole 8
See this image and copyright information in PMC

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