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L. Danheiser, C. Martinez-Davila, R. J. Auchus, and J. T. Kadonaga, J. Am. Chem. , 1981, 103,2443. F. Sato, S. Iijima, and M. , 1981,22,243. T. Imamoto, Y. Hatanaka, Y. Tawarayama, and M. , 1981,22,4987. H. Sakurai, K. Sasaki, and A. , 1981,22,745. g. Ac Pd(dba), :dppe 1:l Scheme 63 N R ~ Rlw N R ~ NHR~ 9$ 4= 1 (131) iii R' (132) L Reagents: i, CH,=CHMgBr; ii, H,O; iii, SiO, or acidic AI,O, Ally1 vinyl ether derivatives undergo smooth Claisen rearrangement at room temperature on treatment with an excess of EtzAISPh or Et,AlCl-PPh, to give high yields of y,6- unsaturated aldehydes.

1981, 22,3109. D. Jieh Shyh Tsai and D. S. , 1981,22, 2751. General and Synthetic Methods 40 (138) of mainly 2-configuration. 18' Reagents: i, RCHO; ii, (HOCH,CH,),N; iii, H,SO,; iv, KH R R H O A + ii S02Tol . Ho* , A (137) (138) 5 R SnBu"3 (139) Reagents: i, Bu",SnH-AIBN; ii, distillation A particularly successful general approach to 2,4-dienoic acids and their derivatives is to construct an intermediate which, following sigmatropic rearrangement, can undergo elimination to form a diene. The examples shown in Scheme 70 are representative of several new variations on this theme.

Yokota, and M. Kumada, J. Chem. , Chem. , 1981,313. F. Bigi, G. Casiraghi, G. Casnati, and G. Sartori, Synthesis, 1981, 310. R. Bernardi, T. Caronna, S. Morrocchi, P. Traldi, and B. M. Vittimberga, J. Chem. , Perkin Trans. I, 1981, 1607. Saturated and Unsaturated Hydrocarbons 15 Scheme 23 Nakamura and his co-workers have reported that isoprene, in the form of the zirconium complex (45), couples with simple olefins with a remarkably high regioselectivity (>98%) with respect to both olefin and diene.

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