Abstract
Regioselective elimination reactions of 1,2-dibromoalkanes
possessing aryloxy or acyloxy groups at the C-3 position can be
carried out under mild basic conditions to produce the corresponding
2-bromo-1-alkenes. The regioselectivity of these processes is controlled
by the acidity enhancement of hydrogens at C-2 caused by the inductive
electron-withdrawing effects of substituents at C-3. A similar acidity
enhancement of the hydrogens at C-1 causes selective DBU-promoted,
two-step transformations of 1,2-dibromoalkanes to alkyne
derivatives. The 2-bromo-1-alkenes and alkynes, readily prepared
using these regioselective elimination reactions, have been employed
as key intermediates in the synthesis of biologically active natural
products.
1 Introduction
2 Regioselective Elimination
2.1 Simple Synthesis of 2-Bromo-1-alkenes
2.2 Total Synthesis of (-)-Tuliparin B
2.3 Total Synthesis of (+)-Tanikolide
2.4 Total Synthesis of Tremetones
2.5 Elimination Reactions of 1-Acyloxy-4-aryl-2,3-dibromoalkanes
2.6 The Effect of C-4 Electron-Withdrawing Groups on HBr Elimination
Reactions
3 Alkyne Synthesis
3.1 Two-Step Elimination Reactions with DBU
3.2 Total Synthesis of (-)-Muricatacin and (-)-(R ,R )-Sapinofuranone
B
4 Summary
Key words
bromoalkenes - alkynes - dibromoalkanes - regioselective
elimination - acidity enhancement
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