Copper-Catalyzed Borylation/Carboxylation of Alkenes and Alkynes with Carbon Dioxide

铜催化二氧化碳硼化/羧化烯烃和炔烃

• 批准号: 24750047
• 负责人: ZHANG Liang
• 金额: $ 2.91万
• 依托单位: Institute of Physical and Chemical Research
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Young Scientists (B)
• 财政年份: 2012
• 资助国家: 日本
• 起止时间: 2012-04-01 至 2014-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-24750047/
• 关键词: 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

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.

我们已经开发了简单的炔和烯烃与二氧化碳（CO2）的催化硼羰基化的第一个例子。在N-杂环卡宾（NHC）-铜配合物作为催化剂和LiOtBu作为碱的存在下，不饱和底物与二（频哪醇合）二硼和CO2（1 atm）的反应在温和条件下选择性地提供了一个新的β-硼内酯衍生物家族。该反应具有反应底物范围广、区域选择性和立体选择性高等特点，是制备多官能化烃类化合物的理想方法。我们还成功地分离和结构表征了一些关键的反应中间体从逐步化学计量反应的相关NHC-铜配合物。根据实验结果和理论分析，提出了电流反应的可能机理。有关炔的工作已发表在Journal of American Chemical Society上，并在SYNFACTS中突出显示。烯烃研究结果的手稿正在准备中。

项目成果

Transition-Metal-Catalyzed C-C Bond For ming Reactions with Carbon Dioxide, in New and Future Developments in Catalysis (Steven L. Suib Editor)

过渡金属催化的与二氧化碳的 C-C 键形成反应，催化领域的新进展和未来发展（Steven L. Suib 编辑）

• 发表时间: 2013
• 作者: Liang Zhang;Zhaomin Hou
• 通讯作者: Zhaomin Hou

N-Heterocyclic Carbene-Copper Complexes-Catalyzed Carboxylation Reactions with Carbon Dioxide

N-杂环卡宾-铜配合物催化二氧化碳的羧化反应

• 作者: Zhang Liang;Hou Zhaomin
• 通讯作者: Hou Zhaomin

N-Heterocyclic Carbene-Copper Complexes-Catalyzed Boracarboxylation of Alkynes and Alkenes with Diborane and Carbon Dioxide

N-杂环卡宾-铜配合物催化乙硼烷和二氧化碳对炔烃和烯烃的硼羧化反应

• 发表时间: 2013
• 作者: Zhang Liang;Cheng Jianhua;Carry Beatrice
• 通讯作者: Carry Beatrice

Copper-Catalyzed Boracarboxylation of Styrenes with Diborane and Carbon Dioxide

铜催化苯乙烯与乙硼烷和二氧化碳的硼羧化反应

• 发表时间: 2013
• 作者: Liang Zhang;Jianhua Cheng;Beatrice Carry;Zhaomin Hou
• 通讯作者: Zhaomin Hou