Intramolecular oxyallyl-carbonyl (3 + 2) cycloadditions.
Intramolecular oxyallyl-carbonyl (3 + 2) cycloadditions.
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DOI：
10.1021/ja312459b
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发表时间：
2013-04-10
影响因子：
15
通讯作者：
Hsung, Richard P.
中科院分区：
文献类型：
--
作者：
Krenske, Elizabeth H.;He, Shuzhong;Huang, Jian;Du, Yunfei;Houk, K. N.;Hsung, Richard P.
Cycloadditions involving oxyallyl intermediates typically require an electron-rich diene or alkene, but we have discovered the first examples of the cycloaddition of heteroatom-stabilized oxyallyls onto carbonyl groups. An oxazolidinone-substituted oxyallyl undergoes chemoselective (3+2) cycloaddition onto the carbonyl group of a tethered dienone, in preference to formation of the expected (4+3) cycloadduct. Density functional theory calculations indicate that the (3+2) cycloaddition takes place through a concerted, highly asynchronous mechanism. The transition state features simultaneous interactions of the oxyallyl LUMO with the carbonyl π and lone pair orbitals, which place this reaction halfway between a purely pericyclic and a purely pseudopericyclic process (“hemipseudopericyclic”). Further (3+2) cycloadditions involving tethered phenylketones and a tethered enone were predicted theoretically and verified experimentally.
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影响因子：
15
作者：
Birney, DM;Ham, S;Unruh, GR
通讯作者：
Unruh, GR
影响因子：
1.8
作者：
BRAEKMAN, JC;DALOZE, D;DENEUBOURG, F
通讯作者：
DENEUBOURG, F
影响因子：
4.4
作者：
BECKE, AD
通讯作者：
BECKE, AD
DOI：
10.1039/jr9650002009
发表时间：
1965-01-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY
影响因子：
--
作者：
COOKSON, RC;NYE, MJ
通讯作者：
NYE, MJ
影响因子：
15
作者：
Harmata, M;Ghosh, SK;Kirchhoefer, P
通讯作者：
Kirchhoefer, P