- π-Facial selectivities in nucleophilic additions to 4-hetero-tricyclo[5.2.1.02,6]decan-10-ones and 4-hetero-tricyclo[5.2.1.02,6]dec-8-en-10-ones: An experimental and computational study
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Several endo-tricyclo[5.2.1.02,6]decan-10-ones and endo-tricyclo[5.2.1.02,6]dec-8-en-10-ones with hetero atom modifications at the distal C-4 position have been subjected to hydride reduction. π-Face selectivities in these systems are largely governed by the same electronic factors that were earlier identified in the case of the norbornyl system. A computational study demonstrates good predictability at the semi-empirical level.
- Mehta, Goverdhan,Gagliardini, Vanessa,Priyakumar, U.Deva,Sastry, G.Narahari
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- 4-Oxatricyclo[5.2.1.02,6]decan-10-one and 4-oxatricyclo[5.2.1.02,6]dec-8-en-10-one. Experimental and DFT investigations of the π-selectivities
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Ab initio MO and experimental π-selectivities of hydride additions to 4-oxatricyclo [5.2.1.02,6]decan-10-one and 4-oxatricyclo[5.2.1.02,6]dec-8-en-10-one are described. The interactions of σC1-C2 and σC6-C7 with π*C=O, on one hand, and those of σC1-C9 and σC7-C8 with π*C=O, on the other hand, support anti-selectivities for both. This is in full accordance with the experiments. The arguments that are based on electrostatic interactions and electron donation from the ring oxygen do not apply.
- Yadav, Veejendra K.,Balamurugan, Rengarajan
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- Absence of heteroatom kinetic effects in π-routes to carbocations
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In solvolyses of prototypical tricyclic and bicyclic heterocycles, suitably positioned oxygen, nitrogen, or sulfur ring-atoms have little net kinetic influence on π routes to carbocations.
- Nickon, Alex,Jones, Stella S.,Parkhill, Billy J.
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p. 187 - 194
(2007/10/02)
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