The nature of the electronic factor governing diastereofacial selectivity in remotely substituted (X) 2-adamantyl cations: 5-Xversus4-X substitution

Autor:	William Adcock, Neil A. Trout
Rok vydání:	2007
Předmět:	chemistry.chemical_compound Nucleophile Hydride Chemistry Stereochemistry Adamantane Organic Chemistry Electronic effect Alcohol Physical and Theoretical Chemistry Selectivity Hyperconjugation Medicinal chemistry
Zdroj:	Journal of Physical Organic Chemistry. 20:791-798
ISSN:	1099-1395 0894-3230
DOI:	10.1002/poc.1247
Popis:	A limited series of 4eq-substituted (X) 2-methyleneadamantanes (6, YCH2, XF, Cl, Br, I, and SnMe3) has been synthesized and diastereoselectivities for their hydrochlorination (HCl/CH2Cl2) have been determined. Diastereoselectivities for the fluorination (DAST/CH2Cl2) of secondary alcohol mixtures, obtained from the hydride reduction of the precursor ketones (6,YO) to the alkenes, have also been measured. A comparison of this selectivity data for nucleophilic trapping of 4eq-substituted (X) 2-adamantyl cations (4, RH and Me) with the corresponding information for 5-substituted (X) 2-adamantyl cations (1, RH and Me) has revealed important distinctions between the two series. In particular, whereas extended hyperconjugative effects appear to be the predominant electronic effect governing facial selectivity in the 5,2-series, electrostatic influences prevail in the 4,2-disposition. Copyright © 2007 John Wiley & Sons, Ltd.
Databáze:	OpenAIRE
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