Apparent catalytic generation of chiral metal enolates: Enantioselective dienolate additions to aldehydes mediated by Tol-BINAP Cu(II) fluoride complexes

Journal of the American Chemical Society

Volumn 120, Issue 4, 1998, Pages 837-838

  Krüger, Jochen ^a   Carreira, Erick M ^a  

^a CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE; FLUORIDE; METAL;

ARTICLE; CATALYST; CHIRALITY; CONTROLLED STUDY; DRUG SYNTHESIS; ENANTIOMER; NONHUMAN; STEREOCHEMISTRY;

EID: 0038475549     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja973331t     Document Type: Article

References (30)

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3. Recently, Denmark has reported a reaction process with dual activation of nucleophilic and electrophilic reaction partners, see: Denmark, S. E.; Wong, K. T.; Stavenger, R. A. J. Am. Chem. Soc. 1997, 119, 2333.
4. (a) For a report in which the involvement of a Pd enolate is suggested, see: Sodeoka, M.; Ohrai, K.; Shibasaki, M. J. Org. Chem. 1995, 60, 2648 and references therein
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6. Related processes wherein putative chiral metal enolates are generated and undergo conjugate additions, isocyanoacetic ester aldol additions, nitroaldols, and enolate animation reactions, see: (a) Sasai, H.; Arai, T.; Satow, Y.; Houk, K. N.; Shibasaki, M. J. Am. Chem. Soc. 1995, 117, 6194. (b) Ito, Y.; Sawamura, M.; Hayashi, T. J. Am. Chem. Soc. 1986, 108, 6405. (c) Sasi, H.; Suzuki, T.; Arai, S.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1992, 114, 4418. (d) Evans, D. A.; Nelson, S. G. J. Am. Chem. Soc. 1997, 119, 6452.
7. Related processes wherein putative chiral metal enolates are generated and undergo conjugate additions, isocyanoacetic ester aldol additions, nitroaldols, and enolate animation reactions, see: (a) Sasai, H.; Arai, T.; Satow, Y.; Houk, K. N.; Shibasaki, M. J. Am. Chem. Soc. 1995, 117, 6194. (b) Ito, Y.; Sawamura, M.; Hayashi, T. J. Am. Chem. Soc. 1986, 108, 6405. (c) Sasi, H.; Suzuki, T.; Arai, S.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1992, 114, 4418. (d) Evans, D. A.; Nelson, S. G. J. Am. Chem. Soc. 1997, 119, 6452.
8. Related processes wherein putative chiral metal enolates are generated and undergo conjugate additions, isocyanoacetic ester aldol additions, nitroaldols, and enolate animation reactions, see: (a) Sasai, H.; Arai, T.; Satow, Y.; Houk, K. N.; Shibasaki, M. J. Am. Chem. Soc. 1995, 117, 6194. (b) Ito, Y.; Sawamura, M.; Hayashi, T. J. Am. Chem. Soc. 1986, 108, 6405. (c) Sasi, H.; Suzuki, T.; Arai, S.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1992, 114, 4418. (d) Evans, D. A.; Nelson, S. G. J. Am. Chem. Soc. 1997, 119, 6452.
9. Related processes wherein putative chiral metal enolates are generated and undergo conjugate additions, isocyanoacetic ester aldol additions, nitroaldols, and enolate animation reactions, see: (a) Sasai, H.; Arai, T.; Satow, Y.; Houk, K. N.; Shibasaki, M. J. Am. Chem. Soc. 1995, 117, 6194. (b) Ito, Y.; Sawamura, M.; Hayashi, T. J. Am. Chem. Soc. 1986, 108, 6405. (c) Sasi, H.; Suzuki, T.; Arai, S.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1992, 114, 4418. (d) Evans, D. A.; Nelson, S. G. J. Am. Chem. Soc. 1997, 119, 6452.
10. (S)-Tol-BINAP is the accepted abbreviation for (S)-(-)-2.2′-bis(di-p-tolylphosphino)-1,1′-binaphthyl, a commercially available diphosphine derivative.
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21. For a report of Ag(I)·BINAP complexes that effect the addition of allyltributyltin and tin enolates to aldehydes, see: Yanagisawa, A.; Nakashima, H.; Ishiba, A.; Yamamoto, H. J. Am. Chem. Soc. 1996, 118, 4723. (b) Yanagisawa, A.; Matsumoto, Y.; Nakashima, H.; Asakawa, K.; Yamamoto, H. J. Am. Chem. Soc. 1997, 119, 9319. It is important to note that these systems prescribe high catalyst loading (10 mol %) and that the Ag(I) complex functions as a Lewis acid without metalation of the nucleophile.
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24. In our intial studies we observed that the use of (S)-BINAP as ligand affords the benzaldehyde aldol adduct in 88% ee and 90% yield. A brief examination of other commercially available diphosphines led to identifying (S)-Tol-BINAP as the ligand which provides optimal selectivities to date.
25. 2 were observed to catalyze the addition of silyldienolates to aldehydes, albeit in diminished levels of asymmetric induction.
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