Copper-catalyzed asymmetric N-H insertion reactions: Couplings of diazo compounds with carbamates to generate α-amino acids

Journal of the American Chemical Society

Volumn 129, Issue 40, 2007, Pages 12066-12067

  Lee, Elaine C ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALPHA AMINO ACID; AMOXICILLIN; AZO COMPOUND; CARBAMIC ACID; COPPER; HYDROGEN; NITROGEN; OXAZOLINE DERIVATIVE; PHENYLGLYCINE; VANCOMYCIN;

ARTICLE; ASYMMETRIC CATALYSIS; CATALYSIS; CHEMICAL REACTION; CHIRALITY; CRYSTALLIZATION; ELECTRON TRANSPORT; ENANTIOSELECTIVITY; EQUILIBRIUM CONSTANT; REACTION ANALYSIS; STEREOCHEMISTRY;

2,2'-DIPYRIDYL; AMINO ACIDS; AZO COMPOUNDS; CARBAMATES; CATALYSIS; COPPER; HYDROGEN; ORGANOMETALLIC COMPOUNDS; STEREOISOMERISM;

EID: 35048874133     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja074483j     Document Type: Article

References (28)

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26. Interestingly, for catalytic asymmetric O-H insertion reactions, the opposite trend is observed: stereoselectivity increases as the steric demand of the ester decreases (ref 9).
27. Notes: (1) An attempt to extend this catalytic asymmetric N-H insertion process to an α-alkyl-α-diazo ester led to a 1,2-H shift, thereby generating an α,β-unsaturated ester. (2) An α-pyridyl-α- diazo ester was unreactive. (3) The reaction of an α-alkenyl-α-diazo ester (2-phenylethenyl) proceeded in good ee (87%), but modest yield (25%). (4) An insertion into the N-H bond of an amine occurred with low enantioselectivity. All of these couplings were conducted under our standard conditions (eq 2) without any optimization.
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