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. 2012 Dec 21;51(52):13054-7.
doi: 10.1002/anie.201207820. Epub 2012 Nov 19.

Ring expansion and rearrangements of rhodium(II) azavinyl carbenes

Nicklas Selander  1 , Brady T Worrell, Valery V Fokin
Affiliations

Ring expansion and rearrangements of rhodium(II) azavinyl carbenes

Nicklas Selander et al. Angew Chem Int Ed Engl. .

Abstract

Room for expansion: an efficient, regioselective, and convergent method for the ring expansion and rearrangement of 1-sulfonyl-1,2,3-triazoles under rhodium(II)-catalyzed conditions is described. These denitrogenative reactions form substituted enaminone and olefin-based products. The enaminone products can be further functionalized to give various heterocycles and ketone derivatives, thus rendering the sulfonyl triazole traceless.

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Figures

Scheme 1
Scheme 1
Utility of Rhodium(II) Azavinyl Carbenes.
Scheme 2
Scheme 2
Rhodium(II)-catalyzed ring expansion and rearrangement of azavinyl carbenes.
Scheme 3
Scheme 3
(A) One-pot large-scale synthesis of 5b. Reaction conditions: 8 (10 mmol, 1 equiv.), 9 (10 mmol, 1 equiv.), CuTc (5 mol%), CHCl3 (15 mL), rt, 4 h; then rhodium(II) octanoate (0.1 mol%), 70 °C, 2 h. (B) Functionalization of 5b. a. PhNH2 (3 equiv), MeOH, rt, 6 h; b. 3-azidopropan-1-amine (2 equiv.), MeOH, rt, 2 h; c. hydrazine-hydrate (5 equiv), MeOH, rt, 1 h; d. Phenyl hydrazine hydrochloride (1.1 equiv), MeOH, rt, 5 h; e. Sulfamide (1.1 equiv), p-TsOH (10 mol%), MeOH, 70 °C, 36 h; See supporting information for reaction details.
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References

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    1. For a recent review of denitrogenative reactions of 1-sulfonyl triazoles see: Chattopadhyay B, Gevorgyan V. Angew Chem Int Ed. 2012;51:862.

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