Ligand-Controlled Palladium-Catalyzed Regiodivergent Defluorinative Allylation of gem-Difluorocyclopropanes via σ-Bond Activation

被引：33

作者：

Wu, Lei ^{[1
]}

Wang, Minyan ^{[1
]}

Liang, Yong ^{[1
]}

Shi, Zhuangzhi ^{[1
,2
]}

机构：

[1] Nanjing Univ, Sch Chem & Chem Engn, State Key Lab Coordinat Chem, Nanjing 210093, Jiangsu, Peoples R China

[2] Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Henan, Peoples R China

来源：

CHINESE JOURNAL OF CHEMISTRY | 2022年 / 40卷 / 19期

基金：

中国国家自然科学基金;

关键词：

Allylation C-C activation Cross-coupling gem-Difluorocyclopropanes Defluorination; DIFLUORINATED CYCLOPROPANES; STEREOSELECTIVE-SYNTHESIS; REDUCTIVE ELIMINATION; DIFLUOROALKENES; FLUORINE; FUNCTIONALIZATION; CARBOXYLATION; BORYLATION; ALKYLATION; HYDRODEFLUORINATION;

D O I：

10.1002/cjoc.202200307

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Comprehensive Summary Monofluoroalkenes are important and versatile privileged components in pharmacologically relevant molecules. Here, we report a method for the selective construction of these compounds in a diversity-oriented fashion through regiodivergent cross-coupling of gem-difluorocyclopropanes with allylboronates by employing a palladium catalyst with two different ligands, in which gem-difluorocyclopropanes were used as allyl electrophiles by C-C and C-F bond activation. In the presence of 2-biphenylyl(diphenyl)phosphine as ligand, the linear-selective allyl-allyl bond formation is highly obtained, while utilizing the sterically hindered BrettPhos (dicyclohexyl[3,6-dimethoxy-2',4',6'-tris(1-methylethyl)[1,1'-biphenyl]-2-yl]phosphine) as the ligand favors the generation of the branched-selective product. Experimental and computational studies investigated the key steps of the cross-coupling reactions, revealing the origin of the ligand-controlled regiodivergence.

引用

页码：2345 / 2355

页数：11

共 121 条

[1] Access to Divergent Fluorinated Enynes and Arenes via Palladium-Catalyzed Ring-Opening Alkynylation of gem-Difluorinated Cyclopropanes [J].