A New Type of Chiral Cyclic Sulfinamide–Olefin Ligands for Rhodium‐Catalyzed Asymmetric Addition. Issue 32 (28th October 2016)

• Record Type: Journal Article
• Authors: Wen, Quan; Zhang, Li; Xiong, Jing; Zeng, Qingle
• Is Part Of: European journal of organic chemistry. Issue 32(2016)
• Page Start: 5360
• Page End: 5364
• Publication Date: 2016-10-28
• Subjects: Addition reactions -- Asymmetric catalysis -- Enantioselectivity -- Ligand design -- Rhodium; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201601206
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : A new type of chiral cyclic sulfinamide–olefin ligands, N ‐allylic 2, 3‐dihydro‐1, 2‐benzoisothiazole 1‐oxides, with 2, 3‐dihydro‐1, 2‐benzoisothiazole 1‐oxide as a unique chiral skeleton, is developed for the highly enantioselective rhodium‐catalyzed asymmetric 1, 4‐addition of α, β‐unsaturated cyclic carbonyl compounds and the 1, 2‐addition of benzil. Both enantiomers of the chiral cyclic sulfinamide–olefin ligand with 99 % ee were easily prepared from inexpensive and commercially available starting materials and were directly used in asymmetric catalysis, and thus, both enantiomers of the addition products could be obtained in high yields (up to 98 %) with excellent enantioselectivities (up to 98 % ee ). Abstract : Rigid and cyclic 2, 3‐dihydro‐1, 2‐benzoisothiazole 1‐oxide acts as chiral skeleton of new chiral sulfinamide–olefin ligands that demonstrate excellent catalytic performance in the Rh‐catalyzed asymmetric 1, 4‐addition of α, β‐unsaturated cyclic carbonyl compounds and the 1, 2‐addition of benzil. Both enantiomers of the ligand are easily prepared, and products are obtained with high ee values for both ligands.