Asymmetric synthesis Negishi reaction

M. Lautens, Science of Synthesis , Georg Thieme Verlag, New York, 2001, Vol. 1, p. 11 E. Negishi, Handbook of Organopalladium Chemistry for Organic Synthesis , Wiley-Interscience, New-York, 2002, Version 2 B. M. Trost and M. L. Crawley, Chem. Rev., 2003, 103, 2921 B. M. Trost and C. Lee, Asymmetric Allylic Alkyaltion Reactions, Catal)4ic Asymmetric Synthesis , Wiley-VCH, 2000, p. 593 A. Pfaltz and M. Lautens, Allylic Substimtion Reactions, Comprehensive Catalysis I-III , Springer, 1999, Vol. 2, p. 833. 

The carbometalation reaction has been reviewed recently [28-30]. Negishi has demonstrated that zirconium(TV) complexes catalyze the carboalumination of MesAl to various alkynes and enynes [31]. Also the Zr-catalyzed asymmetric carboalumination of aUcenes (ZACA reaction) [32-34] has found important applications in the synthesis of natural products [35-37]. Especially efficient was the asymmetric synthesis of insect pheromones such as (S. / ./ ,S. / ,S)-4,6,8,10,16,18-hexamethyl-docosane (88) (Scheme 8) [38]. 

The total synthesis of fluvirucinine A1 127 provides a powerful illustration of the utility of Fu s methodology in natural product synthesis (Scheme 13.34). The asymmetric Negishi reaction of racemic allylic chloride 122 with alkylzinc bromide 123 in the presence of Ni/Pybox catalyst system provided ester 124 in 93% yield and 96% ee. After few steps, the organozinc reagent of bromide 125 was subjected to a second Negishi reaction with chloride 122 under identical coupling conditions to furnish derivative 126 in 80% yield and excellent enantioselectivity. 

Genov M, Fuentes B, Espinet P, Pelaz B. Asymmetric Negishi reaction for sterically hindered couplings synthesis of binaph-talenes. Tetrahedron Asymm. 2006 17(18) 2593-2595. 

Shibasaki M, Miyazaki F (2002) Asymmetric Heck Reactions. In Negishi E, de Meijere A (eds) Handbook of Organopalladium Chemistry for Organic Synthesis. Wiley, New York, p 1283... 

Shibasaki, M., Miyazaki, F. Asymmetric Heck reactions, in Handbook of Organopalladium Chemistry for Organic Synthesis (eds. Negishi, E.-i.,De Meijere, A.), 1, 1283-1315 (Wiley-lnterscience, New York, 2002). 

Scheme 3.45 Efficient and stereoselective synthesis of yellov/ scale pheromone by alkyne haloboration, Zr-catalyzed asymmetric carboalumination of alkenes (ZACA reaction), and Pd-catalyzed tandem Negishi coupling [55].

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