Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, AB, T2N 1N4, Canada.
Department of Chemistry, Nanoscience Centre, University of Jyväskylä, P.O. Box 35, FI-40014 Jyväskylä, Finland.
Chem Commun (Camb). 2022 Jun 1;58(45):6482-6485. doi: 10.1039/d2cc01476a.
Isomeric bis(aldiminium) salts with a 1,4-cyclohexylene framework were synthesized. The first isolable bis(CAAC) was prepared from the -stereoisomer and its ditopic ligand competency was proven by conversion to iridium(I) and rhodium(I) complexes. Upon deprotonation, the -isomer yielded an electron rich olefin a classic, proton-catalyzed pathway. The CC bond formation from the desired -bis(CAAC) was shown to be thermodynamically very favorable and to involve a small activation barrier. Compounds that can be described as insertion products of the -bis(CAAC) into the E-H bonds of NH, CHCN and HO were also identified.
合成了具有 1,4-环己二烯骨架的同手性双(aldiminium)盐。第一个可分离的双(CAAC)是由 -异构体制备的，其双位点配体能力通过转化为铱(I)和铑(I)配合物得到证明。脱质子后，-异构体生成富电子烯烃，这是一种经典的质子催化途径。从所需的 -双(CAAC)形成 C-C 键在热力学上非常有利，并且涉及小的活化能垒。还确定了可以描述为 -双(CAAC)插入 NH、CHCN 和 HO 的 E-H 键的插入产物的化合物。
