Alkenyl Isocyanide Conjugate Additions: A Rapid Route to γ-Carbolines.
Alkenyl Isocyanide Conjugate Additions: A Rapid Route to γ-Carbolines.
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DOI：
10.1002/anie.201612574
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发表时间：
2017-04-03
期刊：
影响因子：
--
通讯作者：
Fleming FF
中科院分区：
文献类型：
--
作者：
Chepyshev SV;Lujan-Montelongo JA;Chao A;Fleming FF
异氰化物是特殊的构建块，其在多组分和金属插入反应中的广泛应用掩盖了它们有限的可用性。解决这一不足的是第一种共轭加成-烷基化方法。一系列有机硫化物、镁酸盐、烯醇酸盐和金属氰化物与β-和β，β-二取代芳磺酰基烯基异氰酸酯共轭添加，以快速组装不同的异氰化物支架。中间金属化异氰化物被亲电试剂有效捕获，生成含有连续的三取代中心和四取代中心的取代异氰酸酯。取代的异氰化物被理想地官能化以精制成合成目标，如γ-Caroline，N-甲基异氰酸酯B的三步合成所示。各种有机金属与磺酰取代的烯基异氰酸酯的共轭加成克服了快速组装保留异氰化物官能度的复杂异氰化物的历史挑战。该策略提供了复杂的异氰化物，准备精制成杂环，如N-甲基精氨酸B的三步合成所说明的那样。
Isocyanides are exceptional building blocks whose wide deployment in multi-component and metal insertion reactions belies their limited availability. Addressing this deficiency is the first conjugate addition-alkylation method. An array of organolithiums, magnesiates, enolates, and metalated nitriles, add conjugately to β- and β, β-disubstituted arylsulfonyl alkenyl isocyanides to rapidly assemble diverse isocyanide scaffolds. The intermediate metalated isocyanides are efficiently trapped with electrophiles to generate substituted isocyanides incorporating contiguous tri- and tetra-substituted centers. The substituted isocyanides are ideally functionalized for elaboration into synthetic targets as illustrated by the three-step synthesis of the γ-carboline, N-methyl ingenine B. Conjugate addition of diverse organometallics to sulfonyl-substituted alkenyl isocyanides overcomes the historical challenge of rapidly assembling complex isocyanides that retain the isocyanide functionality. The strategy affords complex isocyanides that are poised for elaboration into heterocycles as illustrated with the three-step synthesis of N-methyl ingenine B.
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影响因子：
5.4
作者：
Chakrabarty, Suravi;Choudhary, Shruti;Doshi, Arpit;Liu, Fa-Qiang;Mohan, Rishabh;Ravindra, Manasa P.;Shah, Dhruv;Yang, Xun;Fleming, Fraser F.
通讯作者：
Fleming, Fraser F.
DOI：
10.1073/pnas.0913307107
发表时间：
2010-03-23
影响因子：
11.1
作者：
Hevia, Eva;Chua, Jonathan Z.;McCall, Matthew D.
通讯作者：
McCall, Matthew D.
影响因子：
16.6
作者：
Merkel, S.;Stern, D.;Stalke, D.
通讯作者：
Stalke, D.
影响因子：
0.6
作者：
Aoyama, Hiroshi;Sako, Kumiko;Hashimoto, Yuichi
通讯作者：
Hashimoto, Yuichi
使用双氧作为氧化剂，通过直接 C-H 键断裂，通过内部炔烃的亚氨基环化，Pd(II) 催化合成咔啉
影响因子：
5.2
作者：
Ding, Shengtao;Shi, Zhuangzhi;Jiao, Ning
通讯作者：
Jiao, Ning