Harada Masato, Kato Shuma, Haraguchi Ryosuke, Fukuzawa Shin-Ichi
Department of Applied Chemistry, Institute of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo, 112-8551, Japan.
Chemistry. 2018 Feb 21;24(11):2580-2583. doi: 10.1002/chem.201706033. Epub 2018 Jan 29.
The Cu(MeCN) PF /DTBM-Segphos complex catalyzed the highly diastereo- and enantioselective 1,3-dipolar cycloaddition of azomethine ylides with benzo[b]thiophene sulfones with the usual regiochemistry to give single isomers of the exo-cycloadducts in good yields. In contrast, the AgOAc/ThioClickFerrophos complex catalyzed the reaction with atypical regiochemistry to give the endo-cycloadducts as major products with excellent enantioselectivities. Thus, the choice of chiral metal complex enabled the regio- and stereoselective synthesis of chiral fused sulfolanes.
Cu(MeCN)PF /DTBM-联苯二酚膦配合物催化甲亚胺叶立德与苯并[b]噻吩砜的高度非对映和对映选择性1,3-偶极环加成反应，以常规区域化学得到外型环加成产物的单一异构体，产率良好。相比之下，AgOAc/硫代ClickFerrophos配合物催化该反应时具有非典型区域化学，以内型环加成产物作为主要产物，对映选择性优异。因此，手性金属配合物的选择实现了手性稠合环丁砜的区域和立体选择性合成。
