2013 Fiscal Year Final Research Report
Copper-Catalyzed Borylation/Carboxylation of Alkenes and Alkynes with Carbon Dioxide
| Project/Area Number |
24750047
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| Research Category |
Grant-in-Aid for Young Scientists (B)
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| Allocation Type | Multi-year Fund |
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| Research Field |
Organic chemistry
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| Research Institution | Institute of Physical and Chemical Research |
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Principal Investigator |
ZHANG Liang 独立行政法人理化学研究所, 侯有機金属化学研究室, 研究員 (20610992)
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| Project Period (FY) |
2012-04-01 – 2014-03-31
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| Keywords | 二酸化炭素 / 銅触媒 / カルベン配位子 / カルボキシル化反応 / ボリル化反応 / アルケン / アルキン |
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| Research Abstract |
We have developed the first example of catalytic boracarboxylation of simple alkynes and alkenes with carbon dioxide (CO2). In the presence of N-heterocyclic carbene (NHC)-copper complexes as a catalyst and LiOtBu as a base, the reaction of unsaturated substrates with bis(pinacolato)diboron and CO2 (1 atm) selectively affords a novel family of beta-boralactone derivatives under mild conditions. The current reaction shows broad substrate scope, high regio- and stereoselectivity for the preparation of multifunctionalized hydrocarbons. We have also successfully isolated and structurally characterized some key reaction intermediates from stepwise stoichiometric reactions of related NHC-copper complexes. Based on the experimental results and rational analysis, a possible mechanism of the current reaction is proposed. The work on alkynes has been published in Journal of American Chemical Society and highlighted in SYNFACTS. The manuscript of the results of alkenes is now in preparation.
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