Base-induced 1,4-elimination: insights from theory and mass spectrometry.

Experimental and theoretical studies on gas-phase base-induced 1,4-elimination reactions are summarized and discussed. The emphasis is on the synergy that is achieved by combining the complementary data from mass spectrometry and theoretical chemistry. The scope and applications of 1,4-eliminations are discussed and compared with other elementary reactions; e.g., 1,2-elimination and aliphatic (S(N)2) and allylic (S(N)2') nucleophilic substitution. Furthermore, the syn versus anti stereochemistry of 1,4-elimination reactions and the effect of E versus Z stereochemistry of the substrate are examined. Particular attention is paid to the mechanistic nature of 1,4-elimination, i.e., E2 or E1cb, as well as special features such as the single-well E2 and E1cb mechanism. Also, new results from density functional theory computations (BP86/TZ2P) are presented. Copyright 2002 Wiley Periodicals, Inc.