Spokoyny Alexander M, Lewis Calvin D, Teverovskiy Georgiy, Buchwald Stephen L
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, United States.
Organometallics. 2012 Dec 24;31(24):8478-8481. doi: 10.1021/om301116x.
We have prepared the first examples of B9-connected trivalent aryl and alkyl phosphinoborane species via Pd-catalyzed phosphination of 9-iodo--carborane. Our studies highlight the unique electronic features of the B9-connected -carboranyl moiety as compared to its C1-based analogue. This work suggests that the B9-functionalized -carboranyl substituent in these ligands exhibits more electron-releasing character than any other known carbon-based substituent, ultimately laying the foundation for a new class of phosphine ligands with extremely electron-rich character.
我们通过钯催化9-碘-间-碳硼烷的膦化反应，制备了首例与B9相连的三价芳基和烷基膦硼烷物种。我们的研究突出了与基于C1的类似物相比，与B9相连的间-碳硼烷基团独特的电子特性。这项工作表明，这些配体中与B9官能化的间-碳硼烷基取代基比任何其他已知的碳基取代基表现出更强的给电子特性，最终为一类具有极富电子特性的新型膦配体奠定了基础。
