Palladium(0) versus Nickel(0) Catalysis in Selective Functional-Group-Tolerant sp3-sp3 Carbon-Carbon Bond Formations
Palladium(0) versus Nickel(0) Catalysis in Selective Functional-Group-Tolerant sp3-sp3 Carbon-Carbon Bond Formations
复制标题
DOI：
10.1002/chem.200902221
复制
发表时间：
2009-01-01
影响因子：
4.3
通讯作者：
Kobayashi, Shu
中科院分区：
文献类型：
--
作者：
Flegeau, Emmanuel Ferrer;Schneider, Uwe;Kobayashi, Shu
我们发现了Pd-0催化的烯丙基碳酸酯和无毒的烯丙基、丙二烯基或炔丙基硼酸酯之间的分子间不对称Suzuki-Miyaura型sp（3）-sp（3）C-C键形成。本报告代表了这些类型的硼酸酯在这一特定背景下的首次使用。本发明的转化在非常温和的条件下以高选择性进行，并且包括醛官能团的各种官能团被证明是相容的。此外，发现几种硼酸盐显示出非常不寻常的反应性模式，也清楚地证明了与硅相对的硼的更高反应性。最后，与中间体烯丙基-Pd物质相关的β-氢化物消除的固有问题通过使用市售的Ni-0催化剂来解决。
We have uncovered Pd-0-catalyzed intermolecular nonsymmetrical Suzuki-Miyaura-type sp(3)-sp(3) C-C bond formations between allyl carbonates and nontoxic allyl, allenyl, or propargyl boronates. This report represents the first use of these types of boronic esters in this particular context. The present transformations proceeded with high selectivity under remarkably mild conditions, and various functional groups including an aldehyde function proved to be compatible. In addition, several boronates were found to display very unusual reactivity patterns the higher reactivity of boron as apposed to silicon was clearly demonstrated as well. Finally, the inherent problem of beta-hydride elimination associated with intermediary allyl-Pd species was addressed by employing a commercially available Ni-0 catalyst.