Synthesis and Activity of Six-Membered Cyclic Alkyl Amino Carbene–Ruthenium Olefin Metathesis Catalysts

Abstract

General procedures for metathesis reactions…………………………………………………………….20 X-Ray crystallography data for 3c……………………………………………………………...……21-22 X-Ray crystallography data for 3d……………………………………………………………..…….23-24 References…………………………………………………………….………………..…………….…..25 S2 General considerations. Unless otherwise stated, all manipulations were carried out in dry solvents under an atmosphere of argon, using either standard Schlenk techniques or a glovebox. Pentane, toluene, benzene, and diethyl ether were dried using a custom solvent purification system. 4-iodo-2-methylbut-1-ene, 1 1a 2 , and 1b 2 were prepared by literature procedures or slight modifications thereof. Compounds S1,

Syntheses and activities of indol-2-ylidene-ligated ruthenium-based olefin metathesis catalysts

“…The ambiphilicity of IdY was also proved by the longer Ru−O bonds in 2e and 2f (2.313(1) and 2.286(9) Å, respectively) than that in SIMes−Ru (2.261 Å)6 . However, these bonds are significantly shorter than those in Ru−CAAC-5 (~2.33 Å )8 and Ru−CAAC-6 (~2.37 Å)12 . This disagreement can be explained based on the steric effect, which is affected by less sterically hindered Nbenzyl or N-benzhydryl groups.…”

Recent Advances in the Domain of Cyclic (Alkyl)(Amino) Carbenes

“…In addition to the cAAC-5 based ruthenium complexes, cAAC-6 ligands-based ruthenium complexes have also been exploited for their metathesis activity. [65] Lemcoff et al have synthesized photo-switchable Ru catalyst by encasing superior electronic and steric properties of cAAC ligands with latency provided by phosphite ligands. [66] The synthesized catalysts 15, and 16 were tested for a series of olefin metathesis reactions and they gave excellent yield with high stereoselectivity (Scheme 5).…”

Cyclic (Alkyl)(amino)carbenes (CAACs) in Ruthenium Olefin Metathesis

“…Revised manuscript 20 4.7/1) (Scheme 22). 40 The reduced catalytic activity and selectivity were proposed to originate from the increased steric bulk of the CAAC-6 ligand. 28 It is worth noting that allylbenzene resulted in significant olefin migration under the same conditions.…”