Copper-catalyzed asymmetric silylative cyclization of cyclohexadienone-containing 1,6-enynes

Activation of the Si–B interelement bond related to catalysis

“…These authors also reported a copper-catalysed enantioselective silylative cyclization of 1,6-enynes in 2019. 67 Yields were excellent throughout but enantioinduction moderate (165a-k -168a-k, Scheme 47). Here, the authors speculated that coordination of the copper catalyst to the propargylic ether oxygen atom (XQO) steers the regioselectivity of the silylcupration of the alkyne.…”

Fe‐catalyzed hydrohalogenative cyclization of cyclohexadienone‐containing enynes

“…In particular, cyclohexadienone‐containing 1, n ‐enynes are versatile building blocks, readily obtained from oxidative dearomatization of corresponding phenols . A number of cyclization methods with different coupling reagents such as acetic acid, arene C–H, azides bis(pinacolato)diboron, boronic acids, bromodifluoroalkanes, silylacetylenes, and silylboronate were developed for the synthesis of cyclohexenone‐annulated products in a chiral or achiral fashion. In addition, an enantioselective desymmetrization of alkynyl‐cyclohexadienone followed by intermolecular [4 + 2] cycloaddition with activated alkenes to give tricyclic products and reductive cyclization with various hydrogen donors were also reported.…”

Progress in the Synthesis of Hydrobenzofurans from O-Cyclohexadienone-tethered 1,6-Enynes

“…2013 年林国强课题 组 [33] 首次报道了 Cu 催化的环己二烯酮型 1,6-烯炔不对 称硼化/环化反应, 在 Cu 的催化作用下, 联硼酸频哪醇 酯进攻炔丙基醚 β-位, 发生硼化反应得到中间体 D2, 随 后中间体 D2 与环己二烯酮共轭加成得到含有烯基硼酸 酯和烯酮结构的顺式氢化苯并呋喃衍生物(Scheme 13). 国强课题组 [34] 用 CuCl 作为催化剂, PhMe 2 Si-Bpin 作为 硅源, 催化环己二烯酮型 1,6-烯炔不对称硅化环化反应, 制备了一系列硅基化的氢化苯并呋喃衍生物.…”