The Scope and Limitations of Intramolecular Nicholas and Pauson-Khand Reactions for the Synthesis of Tricyclic Oxygen- and Nitrogen-Containing Heterocycles
The Scope and Limitations of Intramolecular Nicholas and Pauson-Khand Reactions for the Synthesis of Tricyclic Oxygen- and Nitrogen-Containing Heterocycles
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DOI：
10.1021/jo8027592
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发表时间：
2009-05-15
影响因子：
3.6
通讯作者：
Shea, Kevin M.
中科院分区：
文献类型：
--
作者：
Closser, Kristina D.;Quintal, Miriam M.;Shea, Kevin M.
We studied the scope and limitations of a tandem intramolecular Nicholas/Pauson-Khand strategy for the synthesis of tricyclic oxygen- and nitrogen-containing heterocycles. This methodology enables conversion of simple acyclic starting materials into a series of previously unknown heterocyclic architectures. For the preparation of cyclic ethers (Z = 0), tricyclic [5,6,5]- through [5,9,5]-systems (m = 1, n = 1-4) are available with the [5,7,5]- and [5,8,5]-systems amenable to quick and efficient synthesis. Tricyclic [5,7,5]- and [5,8,5]-amine-containing (Z = NTs) heterocycles can be successfully prepared. Attempts to make larger ring systems (Z = 0, m = 2; Z = 0, n = 5; or Z = NTs, n = 4-5) or prepare lactones via Nicholas reactions with carboxylic acid nucleophiles (available via oxidation of alcohol nucleophiles, Z = 0) result in decomposition or dimerization. The latter process enables formation of 14-, 16-, and 18-membered ring diolides when using carboxylic acid nucleophiles. We also investigated the use of chiral amine promoters in the Pauson-Khand step but found no asymmetric induction.
