Departamento de Química Orgánica (Universidad de Sevilla) and Centro, de Innovación en Química Avanzada (ORFEO-CINQA), C/ Prof. García González 1, 41012, Sevilla, Spain.
Instituto Investigaciones Químicas (CSIC-US) and Centro de Innovación en Química Avanzada (ORFEO-CINQA), C/ Américo Vespucio 49, 41092, Sevilla, Spain.
Chemistry. 2020 Jan 13;26(3):629-633. doi: 10.1002/chem.201905078. Epub 2019 Dec 17.
The formal insertion of alkenes into aromatic chloro- and bromoalkynes takes place under cationic gold catalysis. This haloalkynylation reaction can be performed with cyclic, gem-disubstituted and monosubstituted alkenes, using BINAP, triazolo[4,3-b]isoquinolin-3-ylidene ligands or SPhos, respectively. The products were isolated in moderate to excellent yields and with complete diastereo- and regioselectivity; the halogen atom bonding the more substituted carbon of the alkene. Preliminary experiments showed that the enantioselective haloalkynylation of cyclopentene can be performed with (S)-BINAP to afford the insertion products with moderate to good enantioselectivities.
烯键在阳离子金催化下正式插入芳基氯代和溴代炔烃中。该卤代炔烃化反应可分别使用 BINAP、三唑并[4,3-b]异喹啉-3-亚基、SPhos 配体，用环状、双取代和单取代烯烃进行。产物以中等至优异的产率和完全的非对映选择性和区域选择性分离；卤素原子与烯键连接取代程度较高的碳。初步实验表明，（S）-BINAP 可实现环戊烯的对映选择性卤代炔烃化，得到具有中等至良好对映选择性的插入产物。
