Denolf Bram, Mangelinckx Sven, Törnroos Karl W, De Kimpe Norbert
Department of Organic Chemistry, Faculty of Bioscience Engineering, Ghent University, Belgium.
Org Lett. 2006 Jul 6;8(14):3129-32. doi: 10.1021/ol0611245.
[reaction: see text] Reaction of chiral alpha-chloro tert-butanesulfinyl aldimines with Grignard reagents efficiently afforded beta-chloro N-sulfinamides in high diastereomeric excess. The latter compounds were cyclized toward the corresponding chiral aziridines in a high-yielding one-pot reaction or after separate treatment with base. The diastereoselectivity obtained in the newly synthesized beta-chloro sulfinamides is explained via the coordinating ability of the alpha-chloro atom with magnesium resulting in the opposite stereochemical outcome as generally observed for nonfunctionalized N-sulfinyl imines.
[反应：见正文] 手性α-氯叔丁基亚磺酰醛亚胺与格氏试剂反应能高效地以高非对映体过量得到β-氯-N-亚磺酰胺。后者的化合物在高产率的一锅反应中或在用碱单独处理后环化生成相应的手性氮丙啶。新合成的β-氯亚磺酰胺中获得的非对映选择性是通过α-氯原子与镁的配位能力来解释的，这导致了与未官能化的N-亚磺酰亚胺通常观察到的相反立体化学结果。
