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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

    1. Rhodium(II)-catalyzed ring expansions: Padwa A, Kulkarni YS, Zhang Z. J Org Chem. 1990;55:4144.Pellicciari R, Natalini B, Sadeghpour BM, Marinozzi M, Snyder JP, Williamson BL, Kuethe JT, Padwa A. J Am Chem Soc. 1996;118:1.Damour D, Renaudon A, Mignani S. Synlett. 1995:111.Chen S, Zhao Y, Wang J. Synthesis. 2006:1705.Xu H, Zhang W, Shu D, Werness JB, Tang W. Angew Chem Int Ed. 2008;47:8933.For a recent example of a chiral Lewis acid-catalyzed ring expansion see: Hashimoto T, Naganawa Y, Maruoka K. J Am Chem Soc. 2011;133:8834.Rhodium(II)-catalyzed rearrangements: Nagao K, Chiba M, Kim S-W. Synthesis. 1983:197.Nagao K, Yoshimura I, Chiba M, Kim S-W. Chem Pharm Bull. 1983;31:114.Pellicciari R, Natalini B, Cecchetti S, Fringuelli R. Steroids. 1987;49:433.Baudouy R, Core J, Ruest L. Tetrahedron. 1987;43:1099.Ye T, McKervey MA. Tetrahedron. 1992;48:8007.Kanemasa S, Kanai T, Araki T, Wada E. Tetrahedron Lett. 1999;49:5055.Vitale M, Lecourt T, Sheldon CG, Aggarwal VK. J Am Chem Soc. 2006;128:2524.Shi W, Xiao F, Wang J. J Org Chem. 2005;70:4318.

    1. Yet L. Chem Rev. 2000;100:2963. - PubMed
    2. Wang YF, Shi QW, Dong M, Kiyota H, Gu Y-C, Cong B. Chem Rev. 2011;111:7652. - PubMed

    1. Recent uses of rhodium-catalyzed ring expansions in synthesis: Wender P, Deschamps N, Sun R. Angew Chem Int Ed. 2006;3957Frey B, Wells AP, Rogers DH, Mander LN. J Am Chem Soc. 1998;120:1914.Kane JL, Shea KM, Crombie AL, Danheiser RL. Org Lett. 2001;3:1081.Liu R, Zhang M, Wyche TP, Winston-McPherson GN, Bugni TS, Tang W. Angew Chem Int Ed. 2012;51:7503.

    1. Recent uses of rhodium(II) azavinyl carbenes: Horneff T, Chuprakov S, Chernyak N, Gevorgyan V, Fokin VV. Am Chem Soc J. 2008;130:14972.Miura T, Yamauchi M, Murakami M. Chem Comm. 2009;12:1359.Chattopadhyay B, Gevorgyan V. Org Lett. 2011;13:3746.Chuprakov S, Kwok SW, Zhang L, Lercher L, Fokin VV. J Am Chem Soc. 2009;131:18034.Grimster NP, Zhang L, Fokin VV. J Am Chem Soc. 2010;13:4870.Chuprakov S, Malik JA, Zibinsky M, Fokin VV. J Am Chem Soc. 2011;133:10352.Miura T, Biyajima T, Fujii T, Murakami M. J Am Chem Soc. 2012;134:194.Selander N, Worrell BT, Chuprakov S, Velaparthi S, Fokin VV. J Am Chem Soc. 2012;134:14670.

    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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