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Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 40, 2010 - Issue 18
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Original Articles

Utilizing the Asymmetric Amino-Cope Rearrangement as a Novel Approach to Enantiomerically Enriched 3-Substituted Aldehydes

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Pages 2696-2711 | Received 05 Jun 2009, Published online: 09 Aug 2010

REFERENCES

  • Allin , S. M. ; Baird , R. D. Development and application of asymmetric [3,3]-sigmatropic rearrangements . Curr. Org. Chem. 2001 , 5 , 395 – 415 , and references cited therein.
  • Allin , S. M. ; Button , M. A. C. ; Shuttleworth , S. J. A tandem amino-Cope rearrangement/enamine alkylation reaction . Synlett. 1997 , 725 – 727 .
  • (a) Allin , S. M. ; Button , M. A. C. The first example of asymmetric induction in an anionic amino-Cope rearrangement . Tetrahedron Lett. 1998 , 39 , 3345 – 3348 ; (b) Allin , S. M. ; Button , M. A. C. ; Baird , R. D. High asymmetric induction in anionic amino-Cope rearrangements controlled by aminoalcohol auxiliaries . Synlett. 1998 , 1117 – 1119 .
  • (a) Allin , S. M. ; Baird , R. D. ; Lins , R. J. Synthetic applications of the amino-Cope rearrangement: Enantioselective synthesis of some tetrahydropyrans . Tetrahedron Lett. 2002 , 43 , 4195 – 4198 ; (b) Allin , S. M. ; Essat , M. ; Horro-Pita , C. ; Baird , R. D. ; McKee , V. ; Elsegood , M. ; Edgar , M. ; Andrews , D. M. ; Shah , P. Applications of the amino-Cope rearrangement: Synthesis of tetrahydropyran, δ-lactone, and piperidine targets . Org. Biomol. Chem. 2005 , 3 , 809 – 815 .
  • Dobson , H. K. ; LeBlanc , R. ; Perrier , H. ; Stephenson , C. ; Welch , T. R. ; Macdonald , D. [1,3]- and [3,3]-rearrangement of 3-amino-1,5-hexadienes: Solvent effect on the regioselectivity . Tetrahedron Lett. 1999 , 40 , 3119 – 3122 . It is clear that the sulfur substituent plays a major role in the amino-Cope rearrangement pathway in the work of Dobson et al., because replacement of the thiophenol group by phenol (R1 = OPh) leads to a slight preference for the [3,3]-product in THF/cosolvent mixtures. It has also been noted in oxy-Cope chemistry that although alkoxy substitution in this critical position decelerates the reaction, more importantly it impedes the competing heterolytic cleavage pathway favoured by sulfur.[ 10 ]
  • Yoo , H. Y. ; Houk , K. N. ; Lee , J. K. ; Scialdone , M. A. ; Meyers , A. I. New paradigm for anionic heteroatom Cope rearrangements. J. Am. Chem. Soc. 1998, 120, 205–206.
  • Allin , S. M. ; Button , M. A. C. Evidence for alternative mechanisms in the amino-Cope rearrangement . Tetrahedron Lett. 1999 , 40 , 3801 – 3802 .
  • (a) Evans , D. A. ; Baillargeon , D. J. ; Nelson , J. V. A general approach to the synthesis of 1,6-dicarbonyl substrates: New applications of base-accelerated oxy-Cope rearrangements . J. Am. Chem. Soc. 1978 , 100 , 2242 – 2244 ; (b) Paquette , L. A. ; Reddy , Y. R. ; Vayner , G. ; Houk , K. N. High rate acceleration in oxy-Cope rearrangements induced by sulfur substitution: Kinetic study involving electronically and geometrically differentiated 1-alkenyl-2-(Z-1-propenyl)-7,7-dimethyl-exo-norbornan-2-ols . J. Am. Chem. Soc. 2000 , 122 , 10788 – 10794 .
  • Agami , C. ; Meynier , F. ; Berlan , J. ; Besace , Y. ; Brochard , L. Chiral 3-substituted aldehydes: Determination of absolute configurations and excesses by NMR analysis of derived oxazolidines . J. Org. Chem. 1986 , 51 , 73 – 75 .
  • Haeffner , F. ; Houk , K. N. ; Reddy , Y. R. ; Paquette , L. A. Mechanistic variation and rate effects of alkoxy and thioalkoxy substituents on anionic oxy-Cope rearrangements . J. Am. Chem. Soc. 1999 , 121 , 11880 – 11884 .

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