2003
DOI: 10.1021/ja028984a
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Stereochemical Memory versus Curtin−Hammett Behavior in the Rearrangement of 1,3-Cyclopentanediyl Radical Cations Derived from Housanes through Structural Effects on Conformational Control

Abstract: The electron-transfer-catalyzed rearrangement of the housanes 1 affords regioselectively the two cyclopentenes 2 and 3 by 1,2-migration of a group at the methano bridge. Appropriate ring annelation in the intermediary cyclopentane-1,3-diyl radical cation 1 •+ changes the stereochemical course of the rearrangement from complete stereoselectivity (stereochemical memory) for the structurally simple housane 1b to partial loss of stereoselectivity through competing conformational interconversion for the tricyclic h… Show more

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Cited by 6 publications
(7 citation statements)
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“…In the former stereoselective process, two housane diastereomers are formed, whereas in the latter product-selective case, two distinct products are generated. On the basis of our original publications, , we show that our viscosity approach is particularly appropriate for the elucidation of both stereo- and product-selective transformations. Our incentive for the present Account is to demonstrate the general utility of viscosity as a mechanistic tool and kindle interest among the physical organic chemists in employing it in their mechanistic work.…”
Section: Introductionmentioning
confidence: 89%
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“…In the former stereoselective process, two housane diastereomers are formed, whereas in the latter product-selective case, two distinct products are generated. On the basis of our original publications, , we show that our viscosity approach is particularly appropriate for the elucidation of both stereo- and product-selective transformations. Our incentive for the present Account is to demonstrate the general utility of viscosity as a mechanistic tool and kindle interest among the physical organic chemists in employing it in their mechanistic work.…”
Section: Introductionmentioning
confidence: 89%
“…The reactivity of these short-lived intermediates is controlled by internal (electronic) and external (medium) features; the latter have received little attention to date. Recently we reported on the solvent effects in the rearrangement of the cyclopentane-1,3-diyl radical cation derived from the cyclohexane-annelated housane 3 (Scheme ), with the incentive to demonstrate the general utility of the viscosity approach in acquiring valuable mechanistic details on chemical transformations.
4
…”
Section: Viscosity Dependence Of the Product Selectivity In Radical-c...mentioning
confidence: 99%
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“…Librera and co-workers examined the rearrangement of housane ([2.1.0]bicyclopentane) derived radical cations. 73 Through ring annulation, the conformations of the ring-opened cyclopentane-1,3-diyl radical cations could be controlled, thereby altering the stereochemical outcome of the reaction. In another computational study, substituent effects were examined in the radical cation vinylcyclopropane A cyclopentene rearrangement (eqn.…”
Section: Fragmentation Reactionsmentioning
confidence: 99%