Thermal sigmatropic rearrangements of vinylallenes leading to 11-cis-retinoids and the novel properties of 9-cis, 11-cis, 13-cis-retinal and 11-cis, 13-cis-retinal

CG Knudsen, RAS Chandraratna…

Index: Knudsen, Christopher G.; Chandraratna, Roshantha A. S.; Walkeapaeae, Leslie P.; Chauhan, Yeshpal S.; Carey, Stephen C.; et al. Journal of the American Chemical Society, 1983 , vol. 105, # 6 p. 1626 - 1631

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Citation Number: 26

Abstract

Abstract: The thermally induced [1, 5] sigmatropic hydrogen shift of vinylallene 5 provided a route to highly hindered 1 1-cis-retinoids. The coupling of the hetero cuprate 14 with the propargyl benzoate 13b gave the vinylallene 5, which upon heating (69'C, 2 h) gave three geometrically isomeric retinoids: 11-cis (8), ll-cis, l3-cis (9), and 9-cis, l l-cis, l3-cis (11). The fourth possible geometric isomer, 9-cis, ll-cis (lo), was unstable to the conditions of ...

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