Takeda olefination

Ephritikhine, M. Villiers, C. in Modem Carbonyl Olefination Takeda, T. ed., Wiley-VCH Weinheim, Germany, 2004, 223-285. (Review). 

Ephritikhine, M. Villiers, C. The McMurry Coupling and Related Reactions. In Modem Carbonyl Olefination-, Takeda, T., Ed. Wiley-VCH ... 

The Wittig reaction efficiently olefinates aldehydes and ketones, but not esters or amides. Several early-transition-metal approaches have been taken to this problem. Recently, Takeshi Takeda of the Tokyo University of Agriculture and Technology reported (Tetrahedron Lett. 44 5571,2003) that the titanocene reagent can effect the condensation of an amide 10 with a thioacetal 11 to give the enamine 12. On hydrolysis, 12 is converted into the ketone 13. When the reaction is intramolecular, reduction proceeds all the way, to give the pyrrolidine IS. 

Scheme 6. Carbonyl olefination with titanium-alkylidene species 12 prepared from dithioacetals according to Takeda et al.

Takeda, T. Titanium-based olefin metathesis and related reactions. Titanium and Ziivonium in Organic Synthesis 2002, 475-500. 

The Peterson olefination is a two-step process for the formation of alkenes from an a-silylcarbanion and an aldehyde or ketone. The first step is an addition reaction that affords both syn and anti p-hydroxysilanes. The stereochemistry is then controlled during the elimination step by using either an acid or a base. Reviews Kano, N. Kawashima, T. In Modem Carbonyl Olefination-Methods and Applications Takeda, T. Ed. Wiley-VCH Weinheim, 2004 Chapter 2 The Peterson and Related Reactions, pp. 18-103. (b) Kelly, S. E. In Comprehensive Organic Synthesis Trost, B. M. Fleming, 1., Eds. Pergamon Oxford, 1991 Vol. 1, Chapter 3.1 Alkene Synthesis, pp. 731-737. (c) Ager, D. J. Org. React. 1990, 38, 1-223. (d) Ager, D. J. Synthesis 1984, 384-398. 

However, the apphcability of this cycloaddition is rather limited because of the side reactions such as ene reactions, conjugate addition reactions, and ring opening reactions of the produced cyclobutane derivatives. There was no general Lewis acid-catalyzed [2+2] cycloaddition reaction, until Takeda [25] and Narasaka et al. [26,27,28,29,30,31,32,33] found that alkenyl sulfides react with a wide variety of electron-deficient olefins in the presence of a Lewis acid. 

Takeda, T. Modern Carbonyl Olefination Methods and Applications Wiley-VCH Weinheim, 2004. 

Review Matsubara, S. Oshima, K. In Modern Carbonyl Olefination-Methods and Applications Takeda, T., Ed. Wiley-VCH Weinheim, 2004 Chapter 5 Olefination of Carbonyl Compounds by Zinc and Chromium Reagents, pp. 214-220. 

Takeda, T., Tsubouchi, A. Carbonyl Olefination Utilizing Metal Carbene Complexes in Modern Carbonyl Olefination" Ed. Takeda, T., Wiley-VCH Weinheim, 2004, Chapter 4, p 151-199. 

Synthesis, 11, 1901 (b) Takeda, T. (2004) Modem Carbonyl Olefination, Wiley-VCH Verlag GmbH Co., Weinheim,... 

Edmonds M, Abell A (2004) In Takeda T (ed) Modem carbonyl olefination, Chap. 1. Wiley-VCH, Weinheim... 

Takeda T. Modern carbonyl olefination. Weinheim Wiley-VCH 2004. 

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