535925-40-7Relevant academic research and scientific papers
Mechanistically Guided Design of Ligands That Significantly Improve the Efficiency of CuH-Catalyzed Hydroamination Reactions
Thomas, Andy A.,Speck, Klaus,Kevlishvili, Ilia,Lu, Zhaohong,Liu, Peng,Buchwald, Stephen L.
supporting information, p. 13976 - 13984 (2018/10/25)
Using a mechanically guided ligand design approach, a new ligand (SEGFAST) for the CuH-catalyzed hydroamination reaction of unactivated terminal olefins has been developed, providing a 62-fold rate increase over reactions compared to DTBM-SEGPHOS, the previous optimal ligand. Combining the respective strengths of computational chemistry and experimental kinetic measurements, we were able to quickly identify potential modifications that lead to more effective ligands, thus avoiding synthesizing and testing a large library of ligands. By optimizing the combination of attractive, noncovalent ligand-substrate interactions and the stability of the catalyst under the reaction conditions, we were able to identify a finely tuned hybrid ligand that greatly enables accelerated hydrocupration rates with unactivated alkenes. Moreover, a modular and robust synthetic sequence was devised, which allowed for the practical, gram-scale synthesis of these novel hybrid ligand structures.
Enantioselective Rhodium-Catalyzed Atom-Economical Macrolactonization
Ganss, Stephanie,Breit, Bernhard
, p. 9738 - 9742 (2016/08/10)
A highly attractive route toward macrolactones, which form the cyclic scaffold of a multitude of diverse natural compounds, is described. Although many chemical approaches to this structural motif have been explored, an asymmetric variant of the cyclization is unprecedented. Herein we present an enantioselective macrolactonization through an intramolecular atom-economical rhodium-catalyzed coupling of ω-allenyl-substituted carboxylic acids. The use of a modified diop ligand, chiral DTBM-diop, led to high enantioselectivity (up to 93 % ee). The reaction tolerated a large variety of functionalities, including α,β-unsaturated carboxylic acids and depsipeptides, and provided the desired macrocycles with very high enantio- and diastereoselectivity.
Process research on the asymmetric hydrogenation of a benzophenone for developing the manufacturing process of the squalene synthase inhibitor TAK-475
Goto, Mitsutaka,Konishi, Takahiro,Kawaguchi, Shinji,Yamada, Masatoshi,Nagata, Toshiaki,Yamano, Mitsuhisa
experimental part, p. 1178 - 1184 (2011/12/16)
A practical synthetic method for the synthesis of the chiral benzhydrol 8, which is the key intermediate of the squalene synthase inhibitor TAK-475 (1), has been developed. The method, via asymmetric hydrogenation of the benzophenone 7, employed Noyori's ruthenium precatalyst of the type [RuCl 2(diphosphine)(diamine). We focused on tuning of the chiral diphosphine, and have discovered a novel ligand, DADMP-BINAP (18c), for the catalyst that has allowed reduction of the operating pressure in the asymmetric hydrogenation. The precatalyst containing 18c performed effectively at low hydrogen pressure (1 MPa) with sufficient enantioselectivity, and the result enabled us to successfully obtain enantiomerically pure 8 on a multikilogram scale.
TRANSITION METAL COMPLEX HAVING DIPHOSPHINE COMPLEX AS LIGAND
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Page/Page column 13, (2010/02/13)
A transition metal complex having 2,2'-bis[bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphino]-1,1'-binaphthyl as a ligand. The presence of the transition metal complex in the reaction system of an asymmetric reaction system allows the preparation of an objective compound having an objective absolute configuration with improved efficiency.
PROCESS FOR PREPARATION OF DIPHOSPHINE COMPOUNDS AND INTERMEDIATES FOR THE PROCESS
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Page 27, (2008/06/13)
A production method of a_compound represented by the formula wherein R1a, R1b, R1c, R1d, R1e, R1f, R2a, R2b, R2c R2d, R2e and R2f are the same or different and each is a hydrogen atom and the like, and R3, R4, R5, R6, R7, R8, R9 and R10 are the same or different and each is a hydrogen atom and the like, or a salt thereof, which comprises reacting a compound represented by the formula wherein X is a leaving group and other symbols are as defined above, or a salt thereof, with a phosphine-borane complex represented by the formula wherein the symbols are as defined above, or a salt thereof, in a solvent in the presence of an amine and a nickel catalyst, is provided.
