Highly efficient Rh(I)/tris-binaphthyl monophosphite catalysts for hydroformylation of sterically hindered alkyl olefins

被引：12

作者：

Costa, Goncalo N. ^{[1
,2
]}

Carrilho, Rui M. B. ^{[1
]}

Dias, Lucas D. ^{[1
]}

Viana, Julio C. ^{[3
]}

Aquino, Gilberto L. B. ^{[1
,3
]}

Pineiro, Marta ^{[1
]}

Pereira, Mariette M. ^{[1
]}

机构：

[1] Univ Coimbra, Dept Chem, CQC, P-3004535 Coimbra, Portugal

[2] Luzitin SA, Edificio Bluepharma, P-3045016 Coimbra, Portugal

[3] State Univ Goias, Exact Sci & Technol Unit, Fac Pharm, BR-75132400 Anapolis, Goias, Brazil

来源：

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL | 2016年 / 416卷

关键词：

Rhodium/tris-binaphthyl monophosphite; Hydroformylation; Substituted alkyl olefins; Terpenes; Steroids; ASYMMETRIC HYDROFORMYLATION; BULKY PHOSPHITE; FRAGRANCE COMPOUNDS; RHODIUM; LIGANDS; OILS; COMPLEXES; TRANSESTERIFICATION; MONOTERPENES; BIODIESEL;

D O I：

10.1016/j.molcata.2016.02.016

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The hydroformylation of highly substituted alkyl olefins was efficiently performed, with use of rhodium(I)/tris-binaphthyl monophosphite catalysts, containing different ether substituents at the 2'-binaphthyl position (OMe, OBn, OCHPh2 and OAdamantyl). A systematic kinetic study, carried out for hydroformylation of methyl non-3-enoate, has shown a significant influence of the ligand's OR group in the performance of the rhodium catalysts, with Rh(I)/tris[2'-benzyloxy-1,1'-binaphthyl-2-yl]phosphite catalytic system (Rh(I)/L2-OBn) achieving the highest chemoselectivity for aldehydes, and regioselectivity for C-5 formyl products. This catalytic system was further applied to the hydroformylation of encumbered C-C double bonds of natural products, namely oleic acid methyl ester, (-)-isopulegol benzyl ether and 17 beta-acetoxyandrost-4-ene, obtaining high catalytic activity, chemo-, regio- and diastereoselectivity, under relatively mild reaction conditions. (C) 2016 Elsevier B.V. All rights reserved.

引用

页码：73 / 80

页数：8

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