Institute of Drug Discovery Technology, Ningbo University, Ningbo 315211, Zhejiang, China.
Mulliken Center for Theoretical Chemistry, Clausius Institut für Physikalische und Theoretische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Beringstrasse 4, 53115 Bonn, Germany.
Chem Commun (Camb). 2023 May 18;59(41):6191-6194. doi: 10.1039/d3cc01571h.
Reactions of (BuOCN) with FLPs are examined. B(CF) interacts with the carbonyl oxygen atoms inducing loss of CHCMe; however, in the presence of basic donors, the protons are intercepted affording the salts [Hbase] [((CF)BOCN)] (base = BuP 1, NCHPh2, HNCHMe3). In contrast, in the presence of (-Tol)P, a proton transfers to the diazo-N atom affording (-Tol)PN(COBu)NHB(CF)4. Further addition of B(CF) to 4 prompts loss of olefin CHCMe and CO affording (-Tol)PNHNHB(CF)5. The course of these reactions is examined by extensive DFT calculations. The nature of 5 is consistent with the FLP reduction of a diazene fragment.
（BuOCN）与 FLP 的反应被研究。B(CF) 与羰基氧原子相互作用，导致 CHCMe 的丢失；然而，在碱性供体存在下，质子被截获，生成盐 [Hbase] [((CF)BOCN)]（base = BuP 1、NCHPh2、HNCHMe3）。相比之下，在 (-Tol)P 的存在下，质子转移到重氮氮原子上，生成 (-Tol)PN(COBu)NHB(CF)4。进一步向 4 中添加 B(CF)，会导致烯烃 CHCMe 和 CO 的丢失，生成 (-Tol)PNHNHB(CF)5。这些反应的过程通过广泛的 DFT 计算进行了研究。5 的性质与 FLP 还原二氮烯片段一致。
