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Eliminations from Olefins
Author(s) -
Köbrich G.
Publication year - 1965
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.196500491
Subject(s) - chemistry , deprotonation , elimination reaction , dehydrohalogenation , medicinal chemistry , steric effects , ether , halogenation , aryl , ring (chemistry) , acetylene , carbon atom , photochemistry , organic chemistry , catalysis , alkyl , ion
Eliminations from olefins are very often initiated by bases, and usually lead to formation of acetylene derivatives. In view of the numerous side‐reactions and subsequent additions or rearrangments observed, the nature of the base used is of considerable significance. Organometallic bases are very versatile. In addition to dehydrohalogenation, dehalogenation by metals, and also thermolytic and photolytic eliminations. (e.g. the retrodiene reaction with exchange of substituents) are discussed. Elimination from low‐membered cyclic olefins yields cycloalkynes having strained ring‐systems, and the existence of these can be demonstrated by trapping them. The mechanisms known for β‐elimination (E2, E1 and E1cB) occur also in the case of olefins; however – due to the sp2‐hybridization of the carbon atoms taking part – they are realized with different rates of reaction relative to saturated compounds. α‐Eliminations from olefines having aryl residues in the β‐position lead to formation of arylacetylenes by rearrangement of the carbon skeleton. The mechanism of this reaction, which is known as the Fritsch‐Buttenberg‐Wiechell rearrangement, is discussed in considerable detail, and several variations of the reaction are considered. According to present‐day knowledge carbenes are involved in α‐eliminations only when both β‐positions of the olefin are occupied by aliphatic substituents, or when they are occupied by aromatic residues where rearrangement to acetylenes is impossible for steric reasons (as for example with 9‐chloromethylenefluorene). With organolithium compounds a number of dehydrohalogenations, which are formally β‐eliminations, actually proceed via deprotonation on the halogenbearing carbon atom (α‐metallation). α‐Metallations are the rate‐determining steps when ether is used as solvent, but proceed quickly in tetrahydrofuran even at low temperatures. Compounds of the type \documentclass{article}\usepackage{amssymb}\pagestyle{empty}\begin{document}$\raise1pt\hbox{$>$}{\rm C}\raise1pt\hbox{=\kern-3.45pt=}{\rm C(Li)Cl}$\end{document} may be prepared by this method and are recognized as intermediates in α‐eliminations.