Archambeau Alexis, Rovis Tomislav
Department of Chemistry, Colorado State University, Fort Collins, CO 80523 (USA) http://sites.chem.colostate.edu/rovislab.
Angew Chem Int Ed Engl. 2015 Nov 2;54(45):13337-40. doi: 10.1002/anie.201504150. Epub 2015 Sep 11.
Unsaturated N-sulfonamides undergo a Rh(III)-catalyzed allylic C(sp(3))-H activation followed by insertion with an exogenous internal alkyne. The reaction generates [3.3.0], [4.3.0], and [5.3.0] azabicyclic structures with excellent diastereoselectivity. Deuterium labeling experiments implicate a 1,3-Rh shift as a key step in the mechanism.
不饱和N-磺酰胺在铑(III)催化下发生烯丙基C(sp(3))-H活化,随后与外源内炔进行插入反应。该反应生成具有优异非对映选择性的[3.3.0]、[4.3.0]和[5.3.0]氮杂双环结构。氘标记实验表明1,3-铑迁移是该反应机理中的关键步骤。