Why a proximity-induced Diels-Alder reaction is so fast.

Why a proximity-induced Diels-Alder reaction is so fast.
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DOI:
10.1021/ol301083q
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发表时间:
2012-06-15
期刊:
影响因子:
5.2
通讯作者:
Houk, K. N.
Houk, K. N.
中科院分区:
化学1区
文献类型:
--
作者:
Krenske, Elizabeth H.;Perry, Emma W.;Jerome, Steven V.;Maimone, Thomas J.;Baran, Phil S.;Houk, K. N.

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与常规的无环二烯与烯烃的Diels-Alder反应不同,Baran全合成乙烯基双环[2.2.2]辛烯与链烯在室温下发生定量的Diels-Alder反应。密度泛函理论计算表明,这一史无前例的反应活性源于预组织、双烯应变和系绳稳定。
Unlike normal Diels–Alder reactions of acyclic alkadienes with alkenes, the vinylbicyclo[2.2.2]octene employed in the Baran total synthesis of vinigrol undergoes quantitative Diels–Alder reaction with a tethered alkene at room temperature. Density functional theory calculations reveal that this unprecedented reactivity originates from a combination of preorganization, diene strain, and tether stabilization.
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