Bifunctional iridium complex

Sato, Y., Kayaki, Y., and Ikariya, T. (2012) Efficient dynamic kinetic resolution of racemic secondary alcohols by a chemoenzymatic system using bifunctional iridium complexes with C-N chelate amido ligands. Chem. Commun. (Cambridge, UK), 48 (30), 3635-3637. 

In addition to the above computational studies on the mechanism of Ir-catalyzed IV-alkylation reactions, in 2015 Martm-Matute and co-workers [60] also investigated a bifunctional iridium complex-catalyzed iV-alkylation reaction of amines and alcohols by a combination of experimental and computational methods. The mechanisms of Ru- [61], Cu- [62], and Pd-catalyzed [63] IV-alkylation reactions have also been smdied by DFT calculations. 

Bartoszewicz A, Gonzalez Miera G, Martm-Matute B et al (2015) Mechanistic studies on the alkylation of amines with alcohols catalyzed by a bifunctional iridium complex. ACS Catal 5(6) 3704-3716... 

Scheme 4.13 Mechanism of the aniline alkylation with benzyl alcohol catalyzed by bifunctional iridium complex 38.

Chiral epoxides from racemic haloalcohols were efficiently synthesized via a DKR process. The enzyme haloalcohol dehydrogenase was used for the KR of p-haloalcohols to give the enantioenriched epoxide, and the slow reacting enantiomer was racemized with an iridium complex furnishing epoxides in excellent yield and high ee (98%) (Scheme 4.31) [81]. Similarly, several chiral acetates were obtained from racemic secondary alcohols in excellent yields with high enantioselectivities through the use of CALB with bifunctional amidoiridium complexes derived from benzylic amines [82],... 

Hasegawa, Y Gridnev, I. D. Ikariya, T. Enantioselective and Z/E-Selective Conjugate Addition of a-Substituted Cyanoacetates to Acetylenic Esters Catalyzed by Bifunctional Ruthenium and Iridium Complexes. Angew. Chem. Int Ed. 2010,49,8157-8160. 

In this chapter, I outline our recent progress in asymmetric reductive and oxidative transformations with bifunctional molecular catalysts based on ruthenium, rhodium, and iridium complexes bearing chiral chelating amine ligands. 

Suzuki T, Morita K, Matsuo Y, Hiroi K. Catalytic asymmetric oxidative lactonizations of meso-diols using a chiral iridium complex. Tetrahedron Lett. 2003 44 2003—2006. Moritani J, Hasegawa Y, Kayaki Y, Ikariya T. Aerobic oxidative desymmetrization of meso-diols with bifunctional amidoiridium catalysts bearing chiral N-sulfonyldiamine ligands. Tetrahedron Lett. 2014 55 1188-1191. 

The dimerization of functional alkenes such as acrylates and acrylonitrile represents an attractive route to obtain bifunctional compounds such as dicarboxylates and diamine, respectively. The head-to-tail dimerizahon of acrylates and vinyl ketones was catalyzed by an iridium hydride complex generated in situ from [IrCl(cod)]2 and alcohols in the presence of P(OMe)3 and Na2C03 [26]. The reaction of butyl acrylate 51 in the presence of [IrCl(cod)]2 in 1-butanol led to a head-to-tail dimer, 2-methyl-2-pentenedioic acid dibutyl ester (53%), along with butyl propionate (35%) which is formed by hydrogen transfer from 1-butanol. In order to avoid... 

An amino alcohol-based iridium bifunctional complex 1058 is an efficient catalyst for the formation of dihydrocou-marin from the 1,5-diol 1059 (Equation 412) <20020L2361>. 

The DFT analysis of the mechanism of the iridium-catalyzed alkylation of amines with alcohols by Martin-Matute et al confirmed the bifunctional character of the key [(NHC)lr] complex intermediate 40 (Scheme 4.13), which is cyclometallated by deprotonation of 39 or 42 with an amine or an imine. It is both a proton acceptor at O and a hydride acceptor at Ir. The formadon of 43 is the rate determining step of the catalytic cycle. 

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