Executing and rationalizing the synthesis of a difluorinated analogue of a ring-expanded calystegine B2

Kyne, S. H., Miles, J. A. L., Percy, J. M. and Singh, K. (2012) Executing and rationalizing the synthesis of a difluorinated analogue of a ring-expanded calystegine B2. Journal of Organic Chemistry, 77 (2). pp. 991-998. ISSN 0022-3263

Full content URL: http://pubs.acs.org/doi/ipdf/10.1021/jo2022845

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Abstract

A difluorinated analogue of a ring-expanded calystegine B2 and some N-protected species were prepared via microwave-mediated transannular ring-opening of an epoxyketone. The diastereofacial selectivity of the epoxidation reaction, which delivers the key intermediate, and the regioselectivity of the transannular reactions were analyzed by density functional theory (DFT) methods. The epoxidation stereoselectivity arises from simple steric control, whereas the ring-closure reactions are subject to thermodynamic control.

Keywords:Transannular ring-opening, Density functional theory, Epoxidation reaction
Subjects:F Physical Sciences > F160 Organic Chemistry
F Physical Sciences > F163 Bio-organic Chemistry
Divisions:College of Science > School of Chemistry
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ID Code:17613
Deposited On:10 Jun 2015 14:50

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