Modeling chemical reactivity. 6. Comparison of conformational energy profiles and electrophilic reactivities and stereoselectivities of chiral allylic alcohols and ethers. Evidence against intramolecular hydrogen bonding in allylic alcohols
Conference
·
· J. Am. Chem. Soc.; (United States)
OSTI ID:6613859
Conformational energy profiles for 3-buten-2-ol and 2-methoxy-3-butene, obtained from a uniform level of nonempirical molecular orbital theory, are qualitatively similar; the differences between the two appear to arise primarily because of steric interactions. The lowest energy conformers for both position the OH (OR) group directly over the double bond, casting doubt on the previously advanced interpretation that the equilibrium conformation of the allylic alcohol is directed in part by hydrogen bonding between the hydroxylic hydrogen and the ..pi.. bond. It suggests instead that the conformational biases in both the alcohol and ether are influenced primarily by minimization of oxygen lone pair-..pi.. bond repulsion. Electrostatic potentials indicate a preference for electrophilic attack anti to the OR group in the high-abundance but low-reactivity conformers of 2-methoxy-3-butene and syn to OR in the less abundant but much more reactive conformers, the same preferences as have previously been noted in 3-buten-2-ol. Given that electrophilic addition to allylic alcohols and ethers generally occurs syn to the OH (OR) functionality, the results of the theory support a notion that the overall reaction stereochemistry in these systems is influenced more by relative conformer reactivity than by relative abundance.
- Research Organization:
- Univ. of California, Irvine
- OSTI ID:
- 6613859
- Conference Information:
- Journal Name: J. Am. Chem. Soc.; (United States) Journal Volume: 109:3
- Country of Publication:
- United States
- Language:
- English
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· J. Am. Chem. Soc.; (United States)
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Related Subjects
090210 -- Alcohol Fuels-- Properties-- (1976-1989)
10 SYNTHETIC FUELS
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALCOHOLS
CHEMICAL BONDS
CHEMICAL REACTIONS
CONFORMATIONAL CHANGES
DATA
DOUBLE BONDS
ELEMENTS
ETHERS
HYDROGEN
HYDROXY COMPOUNDS
INFORMATION
MATHEMATICAL MODELS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
STEREOCHEMISTRY
THEORETICAL DATA
10 SYNTHETIC FUELS
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALCOHOLS
CHEMICAL BONDS
CHEMICAL REACTIONS
CONFORMATIONAL CHANGES
DATA
DOUBLE BONDS
ELEMENTS
ETHERS
HYDROGEN
HYDROXY COMPOUNDS
INFORMATION
MATHEMATICAL MODELS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
STEREOCHEMISTRY
THEORETICAL DATA