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- W2307430425 abstract "Stannylcupration of 1-alkynyl ethers with cuprates (Bu3Sn)2Cu(CN)Li2 and Bu3SnCu(CN)Li was studied to develop conditions that yield trans 2and 1-tri-n-butylstannylvinyl ethers stereoand regioselectively in very good yields. Regioselectivity is a function of the reaction conditions. Thus, l t r i -nbutylstannylvinyl ethers are obtained under kinetic conditions (-78 C, THFIMeOH), while trans-2-t ri-n-butylstannylvinyl ethers are obtained under thermodynamic control conditions (0 C, THFIHMPA). Low temperature Hand '3C-NMR studies revealed that the ratios of the stannylvinyl ethers obtained upon work-up are a function of the proportions of the corresponding vinylcopper intermediates, which were spectroscopically identified. Low temperature NMR studies revealed that, when prepared in the presence of HMPA, cuprates such as (Bu3Sn)2Cu(CN)Li2 and Me2Cu(CN)Li2 exist as mixtures with the Gilman-like cuprates [ (Bu3Sn)2CuLi; Me2CuLiI and lithium cyanide. The proportion of Gilman cuprate and lithium cyanide in these mixtures depends on the temperature of cuprate formation and the organic groups in the cuprate. When prepared in THF without HMPA the cyanide of the higher order cyanocuprates is bound in a manner that does not allow its displacement upon addition of HMPA. A new synthesis of 1-alkynyl ethers was developed that involves transformation of an ester into the corresponding enolphosphate by the use of LDA and diethylchlorophosphate followed by elimination using tert-BuLi at -100 C. This procedure is compatible with labile functional groups such as primary chlorides. Stannylvinyl ethers obtained by stannylcupration of 1 -alkynyl ethers proved to be useful synthetic equivalents of acetaldehyde in homologation procedures. Thus, when reacted with aldehydes in the presence of BFs(Et20), a 2-carbon chain extension ensued, stereospecifically producing the corresponding homologated transa, f3-unsaturated aldehydes." @default.
- W2307430425 created "2016-06-24" @default.
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- W2307430425 date "1994-01-01" @default.
- W2307430425 modified "2023-09-27" @default.
- W2307430425 title "Mechanistic, spectroscopic and synthetic investigations of the stannylcupration of alkynyl ethers" @default.
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