No abstract

The Rh(ii)-catalyzed sulfur ylide [1,2]-rearrangement of carbenoids generated from aryldiazoacetates has been realized via N-S bond insertion, generating tertiary sulfides in moderate to excellent yields. This demonstrates the first use of the sulfur ylide [1,2]-rearrangement undergoing N-S bond insertion. This protocol could proceed smoothly with high regioselectivity, low catalyst loading (0.1 mol% Rh2(OAc)4), gram-scale reaction and broad substrate scope. And the product could be converted into glycine derivatives through simple procedures.

A practical and efficient stereoselective synthesis of arylglycine derivatives was realized via palladium-catalyzed α-arylation of a chiral nickel(II) glycinate complex with aryl bromides. The structurally diverse arylglycine products were obtained in excellent isolated yields and with good diastereoselectivity. A simple acidic hydrolysis furnished optically pure arylglycines in high yield, and the chiral ligand (S)-BPB could be efficiently recovered and reused.

Stereoselective Synthesis of Arylglycine Derivatives via Palladium-Catalyzed -Arylation of a Chiral Nickel(II) Glycinate. -Structurally diverse aryl bromides are well tolerated in the -arylation reaction with a chiral nickel(II) glycinate complex. The diastereoisomerically pure nickel(II) arylglycine complexes can be converted to non-naturally occurring arylglycines in high yields and enantiomeric excess. The chiral auxiliary can be recovered and reused. -(ZHANG, F.; SUN, H.; SONG, Z.; ZHOU, S.; WEN, X.; XU, Q.-L.; SUN*, H.; J. Org. Chem. 80 (2015) 9, 4459-4464, http://dx.doi.org/10.

The reaction can be readily scaled up.