Author:
Smith Peter,Donovan William Harley
Abstract
Using aqueous TiCl3-based continuous-flow, radical-generating methods at 25 °C we have carried out a comprehensive EPR study of hydroxyl- and aminyl-radical addition to eight alkene substrates that yielded radicals of general formula XCH2—ĊY—C*HR1R2, where C* is a chiral center, to investigate the magnetic inequivalence of β-CH2 protons arising from a nonadjacent β-C chiral center. We attribute the observed nonequivalence to the long-range influence of the chiral center in these radicals, and note that our results are consistent with the reasonable expectation that the presence of bulky groups in the radicals is likely to favor particular conformations, leading to more easily observed inequivalence of the β-CH2 proton splittings.
Publisher
Canadian Science Publishing
Subject
Organic Chemistry,General Chemistry,Catalysis
Cited by
8 articles.
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1. 4.4.1 R1, R2 and R3: Leading atom is carbon;Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals. Part 1;2007
2. 4.3.7 Secondary alkyl radicals, type R1–ĊH–CR2 3;Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals. Part 1;2007
3. 4.3.4 Secondary alkyl radicals, type R1–CH2–ĊH–CHR2;Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals. Part 1;2007
4. 4.2.2 Primary alkyl radicals, type R2CH–CH2•;Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals. Part 1;2007
5. EPR study of β-methylene proton magnetic inequivalence in monomeric addition radicals derived from mono- and 1,1′-disubstituted ethylenes with chiral and non-chiral substituents;Magnetic Resonance in Chemistry;1995-05