Epoxidation of bromoallenes connects red algae metabolites by an intersecting bromoallene oxide – Favorskii manifold
作者:D. Christopher Braddock、James Clarke、Henry S. Rzepa
DOI:10.1039/c3cc46720a
日期:——
DMDO epoxidation of bromoallenes gives directly α,β-unsaturated carboxylic acids under the reaction conditions. Calculated (ÏB97XD/6-311G(d,p)/SCRF = acetone) potential energy surfaces and 2H- and 13C-labeling experiments are consistent with bromoallene oxide intermediates which spontaneously rearrange via a bromocyclopropanone in an intersecting bromoallene oxide â Favorskii manifold.
DMDO对溴炔烃的环氧化反应在反应条件下直接生成α,β-不饱和羧酸。计算的(ωB97XD/6-311G(d,p)/SCRF = 丙酮)势能面及2H和13C标记实验支持溴炔烃氧化物中间体,这些中间体通过交叉的溴炔烃氧化物-法沃斯基体系自发重排,形成溴环丙酮。