氢键匹配离子对金（I）催化

Martí Àlex, Ogalla Gala, Echavarren Antonio M

Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Av. Països Catalans 16, 43007 Tarragona, Spain.

Departament de Química Orgànica i Analítica, Universitat Rovira i Virgili (URV), C/Marcel·lí Domingo s/n, 43007 Tarragona, Spain.

ACS Catal. 2023 Jul 20;13(15):10217-10223. doi: 10.1021/acscatal.3c02638. eCollection 2023 Aug 4.

The enantioselective reaction of 1,6-enynes with -, -, and -nucleophiles has been developed by matched ion pair gold(I) catalysis in which the chiral gold(I) cation and anion are H-bonded through a urea group. Very high levels of enantiocontrol are achieved (up to >99:1 er) for a broad scope of substrates. DFT studies demonstrate the importance of the H-bond donor group in anchoring the matched chiral cation- and anion-favoring additional noncovalent interactions.

通过匹配离子对金（I）催化实现了1,6-烯炔与α-、β-和γ-亲核试剂的对映选择性反应，其中手性金（I）阳离子和阴离子通过脲基形成氢键。对于广泛的底物，实现了非常高的对映体控制水平（高达>99:1的对映体过量）。密度泛函理论研究表明，氢键供体基团在锚定匹配的手性阳离子和阴离子方面的重要性，有利于额外的非共价相互作用。