Use of Lithiated Chiral o‑Sulfinylbenzyl Carbanions for the One-Pot Building of Linear Fragments Containing up to Four Connected Stereocenters

The reaction of o-sulfinylbenzyl carbanions with prochiral Michael acceptors, such as differently sized cycloalkenones, proceeded with high levels of stereoselectivity, generating molecules containing up to three asymmetric carbon centers in just one synthetic step. All these reactions involved the use of either a proton or an acylating reagent as the final electrophile. Furthermore, the trapping of the enolate resulting from Michael addition with prochiral electrophiles, such as aldehydes or N-sulfonylimines, allowed the highly stereoselective synthesis of densely functionalized compounds containing four chiral centers in just a one-pot sequence, the stereochemical outcome of the sequence being controlled by the sulfinyl auxiliary.邻亚磺酰基苄基碳负离子（o-sulfinylbenzyl carbanions）与前手性迈克尔受体（prochiral Michael acceptors，如不同环尺寸的环烯酮（cycloalkenones））的反应具有高立体选择性，仅通过一步合成即可获得至多含三个手性碳中心（asymmetric carbon centers）的分子。所有该类反应均以质子或酰化试剂（acylating reagent）作为最终亲电试剂（electrophile）。此外，将迈克尔加成（Michael addition）生成的烯醇负离子（enolate）与前手性亲电试剂（例如醛（aldehydes）或N-磺酰亚胺（N-sulfonylimines））进行捕获，可通过一锅法序列（one-pot sequence）高立体选择性地合成多官能团化且含四个手性中心的化合物，该反应序列的立体化学结果由亚磺酰基辅助基（sulfinyl auxiliary）调控。