Enantioselective alkenylation and phenylation catalyzed by a chiral CuF complex

Journal of the American Chemical Society

Volumn 127, Issue 12, 2005, Pages 4138-4139

  Tomita, Daisuke ^a   Wada, Reiko ^a   Kanai, Motomu ^a,b   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

^b JAPAN SCIENCE AND TECHNOLOGY AGENCY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

COPPER COMPLEX; FLUORINE DERIVATIVE; LIGAND;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION; CHEMICAL STRUCTURE; CHIRALITY; ENANTIOSELECTIVITY; REACTION ANALYSIS; SYNTHESIS;

EID: 16244383506     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0507362     Document Type: Article

References (35)

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20. The allylcopper species generated through transmetalation from allylsilane demonstrated completely different reactivity and stability from that prepared through a conventional method (transmetalation from allyllithium or allylmagnesium reagents). For example, CuF-catalyzed allylation proceeded with complete 1,2-selectivity to enones at room temperature (ref 4a).
21. iPr-DuPHOS described in ref 13), and steric effects). The difference between DTBM-SEGPHOS (4) and DMM-SEGPHOS (5) under optimized conditions for enantioselective reaction is also consistent with this tendency: CuF-5 complex (3 mol % in DMF) gave 3aa in only 31% yield for 3 h, while the reaction was completed in 0.5 h using 4 (Table 2, entry 1). This acceleration effect might be due to stabilization of a hypothetical monomeric, active copper species and/or acceleration of the rate-determining ligand exchange (see text) to regenerate the active vinylcopper. For examples of acceleration effects by sterically hindered ligands, see: (a) Littke, A. F.; Schwarz, L.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 6343.
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24. For the substrate scope using the CuF-dppf catalyst, results of mechanistic studies, and the proposed catalytic cycle, see Supporting Information for details.
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30. Simple ketones did not give the addition product at the current stage.
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34. 3 or TBAT as a fluoride source, which demonstrated no catalyst activity.
35. The rate-determining step was identified on the basis of kinetic studies. The order dependencies of the initial reaction rate were 1, 0, and 0.5 regarding CuF, aldehyde, and vinylsilane, respectively.