Addition of Organolithium Reagents to Double Bonds

Yamataka, Hiroshi; Yamada, Ken‐ichi; Tomioka, Kiyoshi

doi:10.1002/9780470682531.pat0310

Cited by 1 publication

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“…The formation of 4 is explained by an initial thiophilic attack of methyllithium, followed by the reaction with a second molecule of 1 a . By contrast, the mechanistic explanation for the formation of thiol 5 is based on the known ability of compounds such as n BuLi for hydride transfer onto CX bonds (X=S, O) 1b. 10 These results are supported by computations suggesting that alkyllithium agents tend to react with 1 a by an initial thiophilic attack.…”

Section: Introductionmentioning

confidence: 99%

Reactions of Cycloaliphatic Thioketones and Their Oxo Analogues with Lithiated Methoxyallene: A New Approach to Vinylthiiranes

Jasiński

Mlostoń

Stolarski

et al. 2014

Chemistry An Asian Journal

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Admantanethione smoothly reacted with lithiated methoxyallene at low temperatures yielding the expected allenyl-substituted thiolate, which upon aqueous work-up underwent spontaneous 1,3-cyclization to afford a hitherto unknown methoxy-substituted vinylthiirane derivative. The analogous reaction with adamantanone led to the corresponding allenyl alcohol that can be isolated and--depending on the conditions applied--either be converted into the corresponding vinyloxirane or into the 2,5-dihydrofuran derivative. Sterically more crowded thioketones were also combined with lithiated methoxyallene, but in these cases competitive 1,5-cyclization leading to isomeric dihydrothiophene derivatives was observed. DFT calculations of model intermediates and products show distinct energy differences of the sulfur and the corresponding oxygen compounds. Desulfurization of the adamantanethione-derived vinylthiirane yielded a methoxy-substituted 1,3-diene that was studied in cycloadditions with electron-deficient dienophiles. Whereas in the case of tetracyanoethylene the corresponding cyclobutane derivative was formed, the reaction with nitrosobenzene provided the expected 1,2-oxazine derivative. By reductive cleavage of the N-O bond this heterocycle was converted into an unsaturated amino alcohol bearing an adamantane moiety.

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Section: Introductionmentioning

confidence: 99%