Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 36, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202208473
Keywords
Alkenylborates; Cobalt Catalysis; Diphosphine Ligands; Hydroboration; Internal Alkynes
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Funding
- National Key R&D Program of China [2021YFA1500200]
- National Natural Science Foundation of China [92156006]
- 111 project of the Ministry of Education of China [B06005]
- Haihe Laboratory of Sustainable Chemical Transformations
- Fundamental Research Funds for the Central Universities
- Frontiers Science Center for New Organic Matter at Nankai University
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In this study, we developed new Co complexes with cyclopropane-based diphosphine ligands that can catalyze highly chemo-, regio-, and stereoselective hydroboration reactions of unsymmetrical internal alkynes. These reactions exhibit unusual regioselectivity, leading to the synthesis of trisubstituted alkenylborates and alkenes with different stereochemistry.
Herein, we report the development of new Co complexes that have cyclopropane-based diphosphine ligands and can catalyze highly chemo-, regio-, and stereoselective hydroboration reactions of unsymmetrical internal alkynes. These reactions exhibited unusual regioselectivity: specifically, reactions of aryl alkyl internal alkynes showed excellent cis-beta-addition selectivity, and reactions of dialkyl internal alkynes gave excellent cis-alpha-addition selectivity. Highly regioselective hydroboration of unsymmetrical dialkyl internal alkynes cannot be achieved by other known methods. The reactions described herein are highly synthetically useful, particularly for the stereoselective synthesis of trisubstituted alkenylborates and alkenes. Mechanistic studies indicate that a Co-I-H species is a plausible active catalyst and the rigid structure of the cyclopropane skeleton of the ligands and the crowded reaction pocket were responsible for the unprecedented regioselectivity.
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