Acetyl Cation Facilitated Cyclizations of Olefinic Aldehydes. III.¹ Factors Determining Regiochemistry in Acroleins

References

• Andersen , N. H. and Uh , H-S. 1973 . Synthetic Commun. , 3 : 115 The syntheses of bulnesol and guaiol using this procedure should be considered as papers I and II of this series: N. H. Andersen and H-S. Uh, Tetrahedron Lett., 2079 (1973)
   Google Scholar
• a)Post-doctoral research associate (9/74-9/75), b) Post-doctoral research associate (4/73-5/76)
   Google Scholar
• Marshall , J. A. and Wuts , P. G. M. 1977 . J. Org. Chem. , 42 : 1794
   Web of Science ®Google Scholar
• Cooper , J. L. and Harding , K. E. 1977 . Tetrahedron Lett. , : 3321
   Google Scholar
• Sodio- and potassiomalonate as well as the tetrabutylammonium derivative were examined in solvents ranging from xylene to HMPT
   Google Scholar
• NMR data supports the inverted stereochemistry assigned to isonitrile XI (See Experimental). Nitrile XII appears to be a mixture of epimeric materials. Upon basic hydrolysis a single acid, the all-equatorial isomer (XIIIa) predominates. Even though gc fails to resolve nitrile XII other studies indicate a mixture
   Google Scholar
• We have observed more than usual production of isonitrile in a number of cyanide displacement reactions on hindered secondary tosylates. In these cases the isonitrile always displays inverted stereochemistry while the nitrile does only to a lesser extent. Nitrile with retention may result from the slower displacement of the isonitrile function
   Google Scholar
• Carr , D. , Seden , T. P. and Turnec , R. W. 1969 . Tetrahedron Lett. , : 477
   Google Scholar
• Johnson , C. R. and Katekar , G. F. 1970 . J. Am. Chem. Soc. , 92 : 5753
   Google Scholar
• Andersen , N. H. and Ladner , D. W. Synthetic Commun. , See: the accompanying article
   Google Scholar
• Ratcliffe , R. and Rodehorst , R. 1970 . J. Org. Chem. , 35 : 4000
   Web of Science ®Google Scholar
• Andersen , N. H. , Uh , H. S. , Smith , S. E. and Wuts , P. G. M. 1972 . J. Chem. Soc., Chem. Commun. , : 956
   Google Scholar
• Marshall , J. A. , Andersen , N. H. and Schlicher , J. W. 1970 . J. Org. Chem. , 35 : 858
   Web of Science ®Google Scholar
• These cadinenes were eventually prepared by the Diels-Alder reaction of ment-3,8-diene (obtained as the exclusive product on reacting neoisopulegyl tosylate with NaCN in HMPT) and acrolein (⊘Me, 100[ddot], 3 hr, 85%), which produces the two endo products shown and none of the regio isomers. The details of this synthesis are available upon request but will not be published since a similar route (using methyl acrylate) has appeared13 since our preliminary account (N. H. Andersen and D. W. Ladner, AGRO-60, 1st No. Amer. Chem. Congress, Dec. 1975)
   Google Scholar
• Buttery , R. G. and Ling , L. C. 1977 . J. Agric. Food Chem. , 25 : 291
   Google Scholar