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1.5-(π-endo) refers to internal position of olefin during 1,5-H transfer, in contrast to the generally observed 1,5-(π-exo)-H transfer
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1.5-(π-endo) refers to internal position of olefin during 1,5-H transfer, in contrast to the generally observed 1,5-(π-exo)-H transfer.
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36
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15844362589
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The ratio of 9a(D)/4a(D) (74%/8%) increases because deuteride is transfered less easily than hydride, and thus, the intramolecular process is favored over the intermolecular one
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The ratio of 9a(D)/4a(D) (74%/8%) increases because deuteride is transfered less easily than hydride, and thus, the intramolecular process is favored over the intermolecular one.
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37
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15844394029
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Atomic coordinates for 9b can be obtained on request from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 IEZ, UK
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Atomic coordinates for 9b can be obtained on request from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 IEZ, UK.
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38
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0026504987
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Reduction of a vinyl radical bearing a t-Bu group has been observed: Journet, M.; Malacria, M. Tetrahedron Lett. 1992, 33, 1893-1896.
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Journet, M.1
Malacria, M.2
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39
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15844425729
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note
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Presumably, the steric effects developed by the bulky tert-butyl and isopropyl groups prevents the usual reduction from occurring. The formation of the heterodiquinene 8c (which has been isolated and characterized) could be explained by an initial 5-endo-trig process followed by a rare β-hydrogen atom abstraction. One of the referees suggested an alternative explanation involving an oxidation of the radical 7 to the corresponding cation which then suffers proton loss.
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40
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0001465664
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equation presented
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The 6-endo-dig cyclization is consistent with the Thorpe-Ingold effect of the bulky diisopropyl group. With a dimethyl group, this process is not observed. See: Magnol, E.; Malacria, M Tetrahedron Lett. 1986, 27, 2255-2256. equation presented
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Magnol, E.1
Malacria, M.2
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41
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15844384392
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A minor quantity of the β-silyl radical incorporated deuterium proving that a 1,5-H transfer is effectively involved in the formation of 6d
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A minor quantity of the β-silyl radical incorporated deuterium proving that a 1,5-H transfer is effectively involved in the formation of 6d.
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42
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33748939157
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(a) Beesley, R. M.; Ingold, C. K.: Thorpe, J. F J. Chem. Soc. 1915, 107, 1080.
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Beesley, R.M.1
Ingold, C.K.2
Thorpe, J.F.3
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