1,2-Carboboration of Arylallenes by In Situ Generated Alkenylboranes for the Synthesis of 1,4-Dienes

被引：6
作者：
Averdunk, Arthur [1 ]
Hasenbeck, Max [1 ]
Mueller, Tizian [1 ]
Becker, Jonathan [2 ]
Gellrich, Urs [1 ]
机构：
[1] Justus Liebig Univ Giessen, Inst Organ Chem, Heinrich Buff Ring 17, D-35392 Giessen, Germany
[2] Justus Liebig Univ Giessen, Inst Anorgan & Analyt Chem, Heinrich Buff Ring 17, D-35392 Giessen, Germany
来源：
CHEMISTRY-A EUROPEAN JOURNAL | 2022年 / 28卷 / 32期
关键词：
1; 2-carboboration; 4-dienes; boranes; density functional theory; Lewis acids; 1,1-CARBOBORATION; ACTIVATION; ALKYNES; BIS(PENTAFLUOROPHENYL)BORANE; B(C6F5)(3); CHEMISTRY; REAGENTS; ALLENES; ACIDS;
D O I：
10.1002/chem.202200470
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
We herein report a novel method for the coupling of unactivated alkynes and arylallenes, which relies on an unprecedented and regioselective 1,2-carboboration of the allene by an alkenylborane. The alkenylborane is conveniently prepared in situ by hydroboration of an alkyne with Piers' borane, i. e., HB(C6F5)(2). The boryl-substituted 1,4-dienes that are formed by this carboboration are well-suited for a subsequent Suzuki-Miyaura coupling with aryl iodides. This allowed us to develop a three-step, one-pot protocol for the synthesis of aryl-substituted 1,4-dienes. The generality of the reaction was demonstrated by the synthesis of twenty dienes with modular variations of all three reaction partners. The mechanism of the new 1,2-carboboration was investigated using dispersion corrected double-hybrid DFT computations that allowed us to rationalize the chemo- and regioselectivity of this key step.
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页数：6
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