Stereoselective Direct Chlorination of Alkenyl MIDA Boronates: Divergent Synthesis of E and Z α‐Chloroalkenyl Boronates. Issue 46 (17th October 2017)

• Record Type: Journal Article
• Authors: Zeng, Yao‐Fu; Ji, Wei‐Wei; Lv, Wen‐Xin; Chen, Yunyun; Tan, Dong‐Hang; Li, Qingjiang; Wang, Honggen
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 46(2017)
• Page Start: 14707
• Page End: 14711
• Publication Date: 2017-10-17
• Subjects: alkenyl boronates -- chlorination -- divergent synthesis -- iterative coupling -- stereoselective synthesis; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201709070
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The individual molecules of α‐chloroalkenyl boronates include both an electrophilic C−Cl bond and a nucleophilic C−B bond, which makes them intriguing organic synthons. Reported herein is a stereodivergent synthesis of both E and Z α‐chloroalkenyl N ‐methyliminodiacetyl (MIDA) boronates through the direct chlorination of alkenyl MIDA boronates using t BuOCl and PhSeCl reagents, respectively. Both reaction processes are stereospecific and the use of sp 3 ‐B MIDA boronate is the key contributor to the reactivity. The synthetic value of the boronate products was also demonstrated. Abstract : One Way or Another : Stereodivergent syntheses of both E and Z α‐chloroalkenyl N ‐methyliminodiacetyl (MIDA) boronates were achieved through the direct chlorination of E ‐alkenyl MIDA boronates using t BuOCl and PhSeCl reagents, respectively. Both reaction processes are stereospecific and the sp 3 ‐B MIDA boronate plays the key role to the reactivity. Broad substrate scope was observed and the synthetic value of the boronate products was demonstrated.