NHC-Cu-catalyzed addition of propargylboron reagents to phosphinoylimines. Enantioselective synthesis of trimethylsilyl-substituted homoallenylamides and application to the synthesis of S-(-)-cyclooroidin.
NHC-Cu-catalyzed addition of propargylboron reagents to phosphinoylimines. Enantioselective synthesis of trimethylsilyl-substituted homoallenylamides and application to the synthesis of S-(-)-cyclooroidin.
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DOI：
10.1021/ja500373s
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发表时间：
2014-03-05
影响因子：
15
通讯作者：
Hoveyda, Amir H.
中科院分区：
文献类型：
--
作者：
Mszar, Nicholas W.;Haeffner, Fredrik;Hoveyda, Amir H.
提出了一种高效、对映选择性加成1-三甲基硅基取代烯片段到磷酰胺的催化方法。在丙基硼试剂的存在下，5.0 mol %的n -杂环碳的铜配合物促进了转化，丙基硼试剂可以很容易地以多克量制备。反应10分钟内，产物收率高达91%，丙烯选择性98%，对映体比例为98:2。各种醛胺作为合适的底物。磷酰基和硅基可以有效地正交去除。硅烯烯部分可以转化为难以通过非硅烯化的烯获得的多用途衍生物。通过海洋生物碱S-(−)-cyclooroidin的简洁对映选择性合成，突出了该方法的特殊功能和实用性。
A catalytic method for the efficient and enantioselective addition of a 1-trimethylsilyl-substituted allene moiety to phosphinoylimines is presented. Transformations are promoted by 5.0 mol % of a copper complex of an N-heterocyclic carbene in the presence of a propargylboron reagent that can be readily prepared in multigram quantities. Within 10 min of reaction, products are obtained in up to 91% yield, 98% allene (vs propargyl) selectivity, and 98:2 enantiomeric ratio. An assortment of aldimines serve as suitable substrates. The phosphinoyl and silyl groups can be removed efficiently and orthogonally. The silylallene moiety may be transformed to versatile derivatives that are difficult to access via nonsilylated allenes. The special features and utility of the approach are highlighted through a succinct enantioselective synthesis of marine alkaloid S-(−)-cyclooroidin.
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影响因子：
8.4
作者：
Movassaghi M;Siegel DS;Han S
通讯作者：
Han S
影响因子：
15
作者：
Reich, HJ;Holladay, JE;Thompson, JL
通讯作者：
Thompson, JL
影响因子：
15
作者：
Vieira, Erika M.;Snapper, Marc L.;Hoveyda, Amir H.
通讯作者：
Hoveyda, Amir H.
影响因子：
5.2
作者：
Fandrick, Keith R.;Ogikubo, Junichi;Senanayake, Chris H.
通讯作者：
Senanayake, Chris H.
影响因子：
1.8
作者：
Patel, Jignesh;Pelloux-Leon, Nadia;Vallee, Yannick
通讯作者：
Vallee, Yannick