Preparation of the Zinc Enolate Equivalent of Amides by Zinciomethylation of Isocyanates: Catalytic Asymmetric Reformatsky-Type Reaction

Abstract

Bis(iodozincio)methane [CH₂(ZnI)₂] transforms isocyanates (R–N=C=O) into the enolate equivalent of amides via zinciomethylation. The reactivity of the enolate equivalent as a nucleophile toward aldehydes depends on the R group of the isocyanate. For the enolate equivalent formed from phenyl isocyanate, the addition of a catalytic amount of an optically active amino alcohol, which acts as an activator, leads to a catalytic asymmetric Reformatsky-type reaction.

Key words

organozinc reagents - dizinc compounds - Reformatsky reaction - asymmetric synthesis - catalysis

• References

• 1a Knochel P, Perea JJ. A, Jones P. Tetrahedron 1998; 54: 8275
• 1b Boudier A, Bromm LO, Lotz M, Knochel P. Angew. Chem. Int. Ed. 2000; 39: 4414
• 1c Knochel P, Leuser H, Gong L.-Z, Perrone S, Kneisel FF. Functionalized Organozinc Compounds . In The Chemistry of Organozinc Compounds . Part 1; Rappoport Z, Marek I. John Wiley & Sons; West Sussex: 2006: 287-393
• 2a Krasovskiy A, Malakhov V, Gavryushin A, Knochel P. Angew. Chem. Int. Ed. 2006; 45: 6040
• 2b Knochel P, Diène C. C. R. Chim. 2011; 14: 842
• 3a Kondo Y, Shilai M, Uchiyama M, Sakamoto T. J. Am. Chem. Soc. 1999; 121: 3539
• 3b Mulvey RE, Mongin F, Uchiyama M, Kondo Y. Angew. Chem. Int. Ed. 2007; 46: 3802
• 4 Wunderlich SH, Knochel P. Angew. Chem. Int. Ed. 2007; 46: 7685
• 5 Knochel P, Schade MA, Bernhardt S, Manolikakes G, Metzger A, Piller FM, Rohbogner CJ, Mosrin M. Beilstein J. Org. Chem. 2011; 7: 1261
• 6a Matsubara S, Oshima K, Utimoto K. J. Organomet. Chem. 2001; 617: 39
• 6b Matsubara S. 1,1-Bismetallated Species . In The Chemistry of Organozinc Compounds . Part 2; Rappoport Z, Marek I. John Wiley & Sons; West Sussex, England: 2006: 641-684
• 6c Matsubara S. J. Synth. Org. Chem., Jpn. 2007; 65: 194
• 7 Sada M, Komagawa S, Uchiyama M, Kobata M, Mizuno T, Utimoto K, Oshima K, Matsubara S. J. Am. Chem. Soc. 2010; 132: 17452
• 8a Sada M, Matsubara S. J. Am. Chem. Soc. 2010; 132: 432
• 8b Takada Y, Nomura K, Matsubara S. Org. Lett. 2010; 12: 5204
• 8c Nomura K, Matsubara S. Chem. Eur. J. 2010; 16: 703
• 9 Yoshino H, Toda N, Kobata M, Ukai K, Oshima K, Utimoto K, Matsubara S. Chem. Eur. J. 2006; 12: 721
• 10 Ooguri A, Ikeda Z, Matsubara S. Chem. Commun. 2007; 4761
• 11 Haraguchi R, Matsubara S. Org. Lett. 2013; 15: 3378
• 12a Orsini F, Pelizzoni F, Ricca G. Tetrahedron 1984; 40: 2781
• 12b Hlavinka ML, Hagadorn JR. Organometallics 2005; 24: 4116
• 13 1,1-Bis(iodozincio)ethane (9) was prepared from 1,1-diiodoethane and zinc using the same method as for the preparation of bis(iodozincio)methane (1). Compared to 1, 9 is unstable and decomposes gradually via β-hydride elimination, even at 25 °C; see: Matsubara S, Mizuno T, Otake Y, Kobata M, Utimoto K, Takai K. Synlett 1998; 1369
• 14 Ganesan K, Brown HC. J. Org. Chem. 1994; 59: 7346
• 15a Oguni N, Omi T. Tetrahedron Lett. 1984; 25: 2823
• 15b Kitamura M, Suga S, Kawai K, Noyori R. J. Am. Chem. Soc. 1986; 108: 6071
• 15c Soai K, Ookawa A, Ogawa K, Kaba T. J. Chem. Soc., Chem. Commun. 1987; 467
• 15d Smaardijk A, Wynberg H. J. Org. Chem. 1987; 52: 135
• 15e Yang X, Shen J, Da C, Wang R, Choi KC. M, Yang L, Wong K. Tetrahedron: Asymmetry 1999; 10: 133
• 16 Lombardo M, Trombini C. The Chemistry of Zinc Enolates . In The Chemistry of Organozinc Compounds . Part 2; Rappoport Z, Marek I. John Wiley & Sons; West Sussex: 2006: 797-861
• 17a Soai K, Oshio A, Saito T. J. Chem. Soc., Chem. Commun. 1993; 811
• 17b Andrés JM, Pedrosa R, Pérez-Encabo A. Tetrahedron 2000; 56: 1217
• 17c Fujiwara Y, Katagiri T, Uneyama K. Tetrahedron Lett. 2003; 44: 6161
• 17d Xu X.-H, Qiu X.-L, Qing F.-L. Tetrahedron 2008; 64: 7353
• 18a Trost BM, Ito H. J. Am. Chem. Soc. 2000; 122: 12003
• 18b Shin E.-k, Kim HJ, Kim Y, Kim Y, Park YS. Tetrahedron Lett. 2006; 47: 1933
• 18c Cozzi PG. Angew. Chem. Int. Ed. 2006; 45: 2951
• 18d Cozzi PG, Mignogna A, Vicennati P. Adv. Synth. Catal. 2008; 350: 975
• 18e Fernández-Ibáñez MÁ, Maciá B, Minnaard AJ, Feringa BL. Angew. Chem. Int. Ed. 2008; 47: 1317
• 19a Soai K, Ookawa A, Kaba T, Ogawa K. J. Am. Chem. Soc. 1987; 109: 7111
• 19b Zhao G, Li X.-G, Wang X.-R. Tetrahedron: Asymmetry 2001; 12: 399
• 20 Demizu Y, Kubo Y, Matsumura Y, Onomura O. Synlett 2008; 433
• 21 Fieser LF, Fieser M. Reagents for Organic Synthesis . Vol. 1. Wiley; New York: 1967: 1276