Department of Chemistry, School of Science, The University of Tokyo, The HFRE Division, ERATO, Japan Science and Technology Agency (JST), Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Chemistry. 2009 Nov 16;15(45):12247-54. doi: 10.1002/chem.200902221.
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.
我们已经发现 Pd(0)催化的非对称Suzuki-Miyaura 型 sp(3)-sp(3) C-C 键形成反应，该反应发生在碳酸烯丙酯和无毒的烯丙基、炔丙基或烯丙基硼酸酯之间。这是首次在这种特定的情况下使用这些类型的硼酸酯。在非常温和的条件下，本转化具有很高的选择性，各种官能团，包括醛基，被证明是相容的。此外，还发现几种硼酸酯显示出非常不寻常的反应性模式；硼的反应性明显高于硅。最后，通过使用商业上可用的 Ni(0)催化剂解决了与中间烯丙基-Pd 物种相关的固有β-氢消除问题。
