Synthesis and application of modular phosphine-phosphoramidite ligands in asymmetric hydroformylation: structure-selectivity relationship.
A series of hybrid phosphine-phosphoramidite ligands has been designed and synthesized in moderate yields from chiral BINOL (1,1'-bi-2-naphthol) or NOBIN (2-amino-2'-hydroxy-1,1'-binaphthyl). They have achieved highly regio- and enantioselectivities in Rh-catalyzed asymmetric hydroformylations of styrene derivatives (branched/linear ratio up to 56.6, ee up to 99 %), vinyl acetate derivatives (up to 98 % ee), and allyl cyanide (up to 96 % ee). Systematic variation of ligand structure showed that the steric factor on the phsophoramidite moiety determined the performance of the ligand. With the increased hindrance, the branched/linear ratio rose, while the ee value dropped in the hydroformylation of styrene. However, the N-substituents did not influence the selectivities much.
Zhang
Xiaowei
X
Department of Chemistry and Chemical Biology and Department of Pharmaceutical Chemistry, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854, USA.
Cao
Bonan
B
Yan
Yongjun
Y
Yu
Shichao
S
Ji
Baoming
B
Zhang
Xumu
X
D002384:Catalysis; D008024:Ligands; D009281:Naphthalenes / Q000737:chemistry; D009284:Naphthols / Q000737:chemistry; D009570:Nitriles / Q000737:chemistry; D009943:Organophosphorus Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010720:Phosphines / Q000737:chemistry*; D012238:Rhodium; D013237:Stereoisomerism; D013329:Structure-Activity Relationship; D020058:Styrene / Q000737:chemistry; D014753:Vinyl Compounds / Q000737:chemistry
D008024:Ligands; D009281:Naphthalenes; D009284:Naphthols; D009570:Nitriles; D009943:Organophosphorus Compounds; D010720:Phosphines; D014753:Vinyl Compounds; C434331:phosphoramidite; D020058:Styrene; C015660:allyl cyanide; C412332:1,1'-bi-2-naphthol; D012238:Rhodium; C044646:phosphine; C011566:vinyl acetate; C412330:1,1'-binaphthyl