title: Modular chiral bidentate phosphonites: design, synthesis, and application in catalytic asymmetric hydroformylation reactions.
abstract: A new class of C2-symmetric chiral bidentate phosphonite ligands has been synthesized in moderate to good yields from readily available starting materials. Application of these air-stable chiral phosphonites in the Rh I-catalyzed asymmetric hydroformylation of styrene derivatives, vinyl acetate, and allyl cyanide afforded the corresponding chiral aldehydes with high regio- and enantioselectivities under mild reaction conditions. The modular nature of the ligands allows fine-tuning of the selectivities through judicious modifications of the substituents on the ligand backbone. X-ray structural analysis of the catalyst precursor suggested that the steric hindrance caused by the protruding remote substituents of the ligands into the vicinity of the metal center might be an important factor for the enantio-control of the reaction, whereas the sense of asymmetric induction can be rationalized on the basis of a trigonal-bipyramidal transition state diagram.
authors.affiliation: State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China.
authors.forename: Baoguo
authors.initials: B
authors.lastname: Zhao
authors.forename: Xingao
authors.initials: X
authors.lastname: Peng
authors.forename: Zheng
authors.initials: Z
authors.lastname: Wang
authors.forename: Chungu
authors.initials: C
authors.lastname: Xia
authors.forename: Kuiling
authors.initials: K
authors.lastname: Ding
mesh_terms: D000475:Alkenes / Q000737:chemistry; D031176:Bidens / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D005561:Formates / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D010720:Phosphines / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D005561:Formates; D008024:Ligands; D010720:Phosphines; C030544:formic acid; D006859:Hydrogen; D012238:Rhodium