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Synlett 2024; 35(15): 1763-1787
DOI: 10.1055/s-0042-1751541
DOI: 10.1055/s-0042-1751541
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Acetal Substitution Reactions: Stereoelectronic Effects, Conformational Analysis, Reactivity vs Selectivity, and Neighboring-Group Participation
The work on this manuscript was supported by the National Institutes of Health (NIH), National Institute of General Medical Sciences (1R35GM148203).
This article is dedicated to Professor Robert Bergman (University of California, Berkeley), a brilliant and creative scientist and scholar, and an outstanding mentor and teacher.
Abstract
Acetal substitution reactions can proceed by a number of mechanisms, but oxocarbenium ion intermediates are involved in many of these reactions. Our research has focused on understanding the conformational preferences, structures, and reactions of these intermediates. This account summarizes our observations that electrostatic effects play a significant role in defining the preferred conformations, and that torsional effects determine how those intermediates react. Neighboring-group effects are not as straightforward as they might seem, considering that oxocarbenium ion intermediates are in equilibrium with structures that involve stabilization by a nearby substituent.
1 Introduction
2 Unexpected Stereoselectivities
3 Determining Conformational Preferences of Oxocarbenium Ions
4 Structures of Carbocations by NMR Spectroscopy and X-ray Crystallography
5 Stereoelectronic Models for Reactions Involving Other Oxocarbenium Ions
6 Stereoselectivity and Reactivity: When They Correlate, When They Do Not
7 Neighboring–Group Participation Is Not as Simple as It Seems
8 What Is True for Carbocations Is True for Carbonyl Compounds
9 Stereoelectronic and Torsional Effects in Reactions of Enolates
10 Summary of Expected Selectivities for Reactions of Cyclic Acetals
11 Conclusion
Key words
acetals - oxocarbenium ion - stereochemical model - neighboring-group effects - addition to carbonyl compounds - enolatesPublication History
Received: 30 September 2023
Accepted after revision: 20 November 2023
Article published online:
16 January 2024
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