Construction of Chiral 1,3-Diamines through Rhodium-Catalyzed Asymmetric Arylation of Cyclic N-Sulfonyl Imines

Abstract

A rhodium/sulfur−olefin complex catalyzed asymmetric 1,2-addition of arylboronic acids to six-membered 1,2,6-thiadiazinane 1,1-dioxide-type cyclic imines to access highly optically active sulfamides (95−99% ee) has been developed. By taking advantage of the simple functional group transformations, an interesting array of valuable chiral 1,3diamines with different substitution patterns can be readily obtained in a highly enantioenriched manner.

An approach to new chiral bicyclic imines and amines via Horner–Wadsworth–Emmons reaction

“…2 Wu et al reported a rhodium-catalyzed asymmetric 1,2-addition of arylboronic acids to six-membered 1,2,6-thiadiazinane 1,1-dioxide-type cyclic imines to afford highly optically active sulfamides (95-99% ee). 3 High diastereoselectivity and enantioselectivity was observed in a [4 + 2] reaction between cyclic sulfonic imine and Boc-protected indole aldehyde yielding polycyclic pyridoindoles. 4 Aza-Darzens reaction of cyclic N-sulfonylimines with a-halogenated ketones provided a variety of tri-and tetrasubstituted aziridines, including benzofused heterocycles as well as spiro-structures in high yields, diastereo-and enantioselectivities (up to >20 : 1 dr and >99.9% ee).…”

Palladium‐Catalyzed Highly Enantioselective Arylation of Cyclic N‐Sulfonyl α‐Ketimino Esters towards the Synthesis of α‐Quaternary Chiral Amino Acid Derivatives

“…Through the use of simple chiral olefin ligands, we have developed highly efficient asymmetric addition to cyclic N ‐sulfonyl imines under rhodium catalysis for accessing a broad range of enantiomerically enriched cyclic amines containing multifunctional groups . Quite recently, we reported construction of an interesting array of valuable chiral 1,3‐diamines through rhodium‐catalyzed asymmetric addition of arylboronic acids to six‐membered 1,2,6‐thiadiazinane 1,1‐dioxide‐type cyclic imines . In connection to this success, we envisaged that the construction of α‐quaternary chiral amino acids might be achieved by designing the corresponding 1,2,6‐thiadiazinane 1,1‐dioxide‐type cyclic α‐iminoesters as new substrates under appropriate transition‐metal catalysis (Scheme ).…”

Rh(I)-Catalyzed Enantioselective Arylation of Cyclic N-Sulfonyl Diketimines Using Planar-Chiral Phosphine-Olefin Ligands Based on a (Cyclopentadienyl)manganese(I) Scaffold with a Highly Fluorinated Aryl Phosphino Group

“…Representative ligands for the asymmetric arylation reactions of cyclic N -sulfonyl ketimines and/or cyclic N -sulfonyl diketimines reported to date are shown in Figure . In the case of reactions employing chiral rhodium catalysts, the use of diene, , sulfur-olefin, phosphite-olefin, bisphosphine, and bis(phosphoramidite) ligands has been reported. In the case of reactions using chiral palladium catalysts, pyridine-oxazoline, chiral palladium catalysts, phosphine-oxazoline, pyridine-hydrazone, imidazoline palladacycle, phosphine-imine, and bis(imidazoline) ligands have been employed.…”

“…In the case of reactions using chiral palladium catalysts, pyridine-oxazoline, chiral palladium catalysts, phosphine-oxazoline, pyridine-hydrazone, imidazoline palladacycle, phosphine-imine, and bis(imidazoline) ligands have been employed. Xu reported the first rhodium-catalyzed enantioselective arylation of cyclic N -sulfonyl diketimines, 1,2,5-thiadiazoline 1,1-dioxide derivatives 1 , by employing a sulfinamide-based olefin ligand (Figure ) and achieved high enantioselectivities . Although these studies have contributed substantially to advances in this field, achieving stereocontrol in new catalytic systems remains a daunting challenge.…”