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Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 43, 2013 - Issue 10
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Original Articles

A Nonenzymatic Kinetic Resolution of (±)-trans-2-Arylcyclohexanols via Esterification Using Polymer-Supported DCC, DMAP, and 3β-Acetoxyetienic Acid

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Pages 1425-1431 | Received 05 Oct 2011, Published online: 05 Mar 2013

REFERENCES

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  • (±)-trans-2-Arylcyclohexanols (±)-1a–e, except 1c (commercially available), were prepared by the reported method: (a) Dumas , F. ; Mezrhab , B. ; d'Angelo , J. ; Riche , C. ; Chiaroni , A. Investigating the π-facial discrimination phenomenon in the conjugate addition of amines to chiral crotonates: A convenient basis for the rational design of chiral auxiliaries. J. Org. Chem. 1996, 61, 2293–2304; (b) Mizuno , M. ; Kanai , M. ; Iida , A. ; Tomioka , K. An external chiral ligand- controlled enantioselective opening of oxirane and oxetane by organolithiums. Tetrahedron 1997, 53, 10699–10708; (c) Basavaiah , D. ; Rao , P. D. Enzymatic resolution of trans-2-arylcyclohexan-1-ols using crude chicken liver esterase (CCLE) as biocatalyst. Tetrahedron: Asymmetry 1994, 5, 223–234; (d) Huitric , A. C. ; Clarke Jr. , W. G. ; Leigh , K. ; Staiff , D. C. Proton magnetic resonance spectra, stereochemistry, and synthesis of 2-(chlorophenyl)cyclohexanols. J. Org. Chem. 1962, 27, 715–719.
  • The 3β-acetoxyetienic acid can be easily prepared from the commercially available pregnenolone acetate (Aldrich; 148.5 USD/25 g): (a) Staunton , J. ; Eisenbraun , E. J. 3β-acetoxyetienic acid . Org. Synth. 1962 , 42 , 4 – 7 ; (b) Djerassi , C. ; Hart , P. A. ; Warawa , E. J. Optical rotatory dispersion studies, 89: The octant rule and the t-butyl group: Synthesis of steroidal t-butyl ketones . J. Am. Chem. Soc. 1964 , 86 , 78 – 85 .
  • Matsugi , M. ; Hagimoto , Y. ; Nojima , M. ; Kita , Y. Effective nonenzymatic kinetic resolution of (±)-trans-2-arylcyclohexanols using 3β-acetoxyetienic acid, DCC, and DMAP . Org. Process Res. Dev. 2003 , 7 , 583 – 584 .
  • For reviews of the nonenzymatic kinetic resolution, see (a) Spivey , A. C. ; Maddaford , A. ; Redgrave , A. J. Asymmetric catalysis of acyl transfer by Lewis acids and nucleophiles: A review . Org. Prep. Proced. Int. 2000 , 32 , 331 – 365 ; (b) Somfai , P. Nonenzymatic kinetic resolution of secondary alcohols . Angew. Chem., Int. Ed. Engl. 1997 , 36 , 2731 – 2733 . For the kinetic resolution of racemic alcohols by using the DCC, see Chinchilla , R. ; Nájera , C. ; Yus , M. ; Heumann , A. Kinetic resolution of racemic carboxylic acids with homochiral alcohols and dicyclohexylcarbodiimide . Tetrahedron: Asymmetry 1991 , 2 , 101 – 104 .
  • The selectivity factor (s) was determined using following equation: s = ln[(1 − C)(1 − ee)] / ln[(1 − C)(1 + ee)], where C is conversion . Kagan , H. B. ; Fiaud , J. C. Topics in Stereochemistry ; Eliel E. L. and Wilen S. H. , (Eds.); Wiley & Sons : New York , 1988 ; vol. 18 , pp. 249 – 330 .
  • For reviws of the CH/π interaction, see (a) Oki , M. 1,9-Disubstituted triptycenes: An excellent probe for weak molecular interactions . Acc. Chem. Res. 1990 , 23 , 351 – 356 ; (b) Etter , M. C. Hydrogen bonds as design elements in organic chemistry . J. Phys. Chem. 1991 , 95 , 4601 – 4610 ; (c) Zaworotko , M. J. Crystal engineering of diamondoid networks . Chem. Soc. Rev. 1994 , 23 , 283 – 288 ; (d) Nishio , M. ; Umezawa , Y. ; Hirota , M. ; Takeuchi , Y. The CH/π interaction: Significance in molecular recognition . Tetrahedron 1995 , 51 , 8665 – 8701 ; (e) Nshio , M. ; Umezawa , Y. ; Hirota , M. The CH/π Interaction, Wiley-VCH: New York, 1998 .

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