Selective Hydroarylation of 1,3‐Diynes Using a Dimeric Manganese Catalyst: Modular Synthesis of Z‐Enynes

• Published in: Angewandte Chemie International Edition Vol. 57; no. 39; pp. 12906 - 12910
• Main Authors: Yan, Zhongfei, Yuan, Xiang‐Ai, Zhao, Yue, Zhu, Chengjian, Xie, Jin
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 24.09.2018; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Alcohols; Alkynes; arylation; Catalysis; Catalysts; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Dimers; homogeneous catalysis; Manganese; Metals; Organic chemistry; Physical Sciences; reaction mechanisms; Science & Technology; Selectivity; RHODIUM; ANNULATION; alkynes; COMPLEXES; reaction mechanisms; TERMINAL ALKYNES; manganese; C-H ACTIVATION; ARYLBORONIC ACIDS; arylation; KETONES; ORGANOBORONIC ACIDS; homogeneous catalysis; CARBONYL; WATER
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201807851

The transition‐metal‐catalyzed selective hydroarylation of unsymmetrical alkynes represents the state‐of‐art in organic chemistry, and still mainly relies on the use of precious late‐transition‐metal catalysts. Reported herein is an unprecedented MnI‐catalyzed hydroarylation of unsymmetrical 1,3‐diyne alcohols with commercially available arylboronic acids with predictive selectivity. This method addresses the challenges in regio‐, stereo‐, and chemoselectivity. It offers a general, convenient and practical strategy for the modular synthesis of multisubstituted Z‐configurated conjugated enynes. This protocol is distinguished by its operational simplicity, complete selectivity, excellent functional‐group compatibility, and gram‐scale potential. A dimeric MnI species, Mn2(CO)8Br2, was proven to be a much more efficient catalyst precursor than Mn(CO)5Br. Doubling up on M n' Mn: Hydroarylation of unsymmetrical 1,3‐diyne alcohols with arylboronic acids, catalyzed by a dimeric MnI catalyst, has been achieved with predictive regio‐, stereo‐, and chemoselectivity. It offers a general, convenient, and practical strategy for the modular synthesis of multisubstituted Z‐configurated conjugated enynes.