Reversing the stereochemistry of a Diels-Alder reaction: use of metalloporphyrin oligomers to control transition state stability

被引：64

作者：

Clyde-Watson, Z ^{[1
]}

Vidal-Ferran, A ^{[1
]}

Twyman, LJ ^{[1
]}

Walter, CJ ^{[1
]}

McCallien, DWJ ^{[1
]}

Fanni, S ^{[1
]}

Bampos, N ^{[1
]}

Wylie, RS ^{[1
]}

Sanders, JKM ^{[1
]}

机构：

[1] Univ Cambridge, Cambridge Ctr Mol Recognit, Chem Lab, Cambridge CB2 1EW, England

来源：

NEW JOURNAL OF CHEMISTRY | 1998年 / 22卷 / 05期

关键词：

D O I：

10.1039/a709199k

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A cyclic Zn-porphyrin trimer with ethyne and butadiyne links stabilises the thermodynamically disfavoured endo transition state and product of a reversible Diels-Alder reaction; at 30 degrees C the endo adduct is formed rapidly and almost exclusively. Linear porphyrin dimers containing ethyne or butadiyne links show related stereochemical preferences to the corresponding cyclic trimers; substantial rate accelerations are observed despite rotational freedom around the linkers. A qualitative correlation is observed between rate acceleration (i.e., transition state binding) and product binding, and the results are rationalised in terms of host geometry and flexibility.

引用

页码：493 / 502

页数：10

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