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Volumn 354, Issue 10, 2012, Pages 1980-1986

Access to both enantiomers of α-chloro-β-keto esters with a single chiral ligand: Highly efficient enantioselective chlorination of cyclic β-keto esters catalyzed by chiral copper(II) and zinc(II) complexes of a spiro-2,2'-bischroman-based bisoxazoline ligand

Author keywords

chloro keto esters; asymmetric catalysis; bisoxazolines; chlorination; copper; zinc

Indexed keywords


EID: 84863676972     PISSN: 16154150     EISSN: 16154169     Source Type: Journal    
DOI: 10.1002/adsc.201200088     Document Type: Article
Times cited : (33)

References (61)
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    • Chiral bisoxazoline complexes of Zn(II) have been used in enantioselective chlorination and fluorination of β-keto phosphonates, a class of closely related chelating carbonyl substrates. See:, L. Bernardi, K. A. Jørgensen, Chem. Commun. 2005, 1324-1326.
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    • Very recently, the Zn(II) complexes of this class of ligands have been shown to be highly efficient in the catalytic asymmetric hydroxylation of β-keto esters, see:, J. Li, G. Chen, Z. Wang, R. Zhang, X. Zhang, K. Ding, Chem. Sci. 2011, 2, 1141-1144.
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    • 2/ 1a also indicated the presence of an 1:1 species along with a significant amount of free ligand 1a (see the Supporting Information), indicating an equilibration of the species in the precatalyst solution. Presumably, an excess of ligand is required to suppress the background reaction promoted by ligand-free and unselective metal centers.
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    • Similar behavior has been observed in bisoxazoline complexes-catalyzed asymmetric fluorination of keto esters, where the choice of the metal salt Cu or Ni has been shown to afford opposite enantioselectivity, see
    • Similar behavior has been observed in bisoxazoline complexes-catalyzed asymmetric fluorination of keto esters, where the choice of the metal salt Cu or Ni has been shown to afford opposite enantioselectivity, see:, N. Shibata, T. Ishimaru, T. Nagai, J. Kohno, T. Toru, Synlett 2004, 1703-1706.
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    • 10) in Zn(II). Chiral bisoxazoline metal-bound substrates with these two geometries can afford opposite selectivity, since rotation of a coordinated substrate by 90° moves its accessible face from the shielded into the unshielded region, and vice versa. For an excellent review, see:, R. Rasappan, D. Laventine, O. Reiser, Coord. Chem. Rev. 2008, 252, 702-714.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.