Instituto de Química Orgánica General (IQOG), CSIC, Juan de la Cierva 3, 28006 Madrid, Spain.
Organic Chemistry Department and Center for Innovation in Advanced Chemistry (ORFEO-CINQA) Universidad Autónoma de Madrid (UAM), 28049 Madrid, Spain.
J Org Chem. 2023 Mar 17;88(6):3697-3713. doi: 10.1021/acs.joc.2c02931. Epub 2023 Mar 3.
The base-induced [2,3]-sigmatropic rearrangement of a series of enantiopure 2-sulfinyl dienes has been examined and optimized using a combination of NaH and PrOH. The reaction takes place by allylic deprotonation of the 2-sulfinyl diene to give a bis-allylic sulfoxide anion intermediate that after protonation undergoes sulfoxide-sulfenate rearrangement. Different substitution at the starting 2-sulfinyl dienes has allowed us to study the rearrangement finding that a terminal allylic alcohol is determinant to achieve complete regioselectivity and high enantioselectivities (90:10-95:5) with the sulfoxide as the only element of stereocontrol. Density functional theory (DFT) calculations provide an interpretation of these results.
一系列手性纯净的 2-亚磺酰二烯经碱诱导的[2,3]-σ重排反应已经过研究，并使用 NaH 和 PrOH 对其进行了优化。该反应通过 2-亚磺酰二烯的烯丙基去质子化进行，生成双烯丙基砜阴离子中间体，然后质子化后发生亚砜-亚磺酸盐重排。起始 2-亚磺酰二烯的不同取代基允许我们研究重排反应，发现末端烯丙醇是实现完全区域选择性和高对映选择性（90:10-95:5）的关键，其中亚砜是唯一的立体控制因素。密度泛函理论（DFT）计算为这些结果提供了解释。
