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Phosphine-Catalyzed Annulations of Azomethine Imines: Allene-Dependent [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] Pathways

Na, Risong and Jing, Chengfeng and Xu, Qihai and Jiang, Hui and Wu, Xi and Shi, Jiayan and Zhong, Jiangchun and Wang, Min and Benitez, Diego and Tkatchouk, Ekaterina and Goddard, William A., III and Guo, Hongchao and Kwon, Ohyun (2011) Phosphine-Catalyzed Annulations of Azomethine Imines: Allene-Dependent [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] Pathways. Journal of the American Chemical Society, 133 (34). pp. 13337-13348. ISSN 0002-7863. PMCID PMC3163120. http://resolver.caltech.edu/CaltechAUTHORS:20111114-153026931

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Abstract

In this paper we describe the phosphine-catalyzed [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] annulations of azomethine imines and allenoates. These processes mark the first use of azomethine imines in nucleophilic phosphine catalysis, producing dinitrogen-fused heterocycles, including tetrahydropyrazolo-pyrazolones, -pyridazinones, -diazepinones, and -diazocinones. Counting the two different reaction modes in the [3 + 3] cyclizations, there are five distinct reaction pathways—the choice of which depends on the structure and chemical properties of the allenoate. All reactions are operationally simple and proceed smoothly under mild reaction conditions, affording a broad range of 1,2-dinitrogen-containing heterocycles in moderate to excellent yields. A zwitterionic intermediate formed from a phosphine and two molecules of ethyl 2,3-butadienoate acted as a 1,5-dipole in the annulations of azomethine imines, leading to the [3 + 2 + 3] tetrahydropyrazolo-diazocinone products. The incorporation of two molecules of an allenoate into an eight-membered-ring product represents a new application of this versatile class of molecules in nucleophilic phosphine catalysis. The salient features of this protocol—the facile access to a diverse range of nitrogen-containing heterocycles and the simple preparation of azomethine imine substrates—suggest that it might find extensive applications in heterocycle synthesis.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja200231vDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja200231vPublisherArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3163120PubMed CentralArticle
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2011 American Chemical Society. Published In Issue August 31, 2011; Article ASAP August 03, 2011; Received: January 21, 2011. This study was supported by the National Natural Science Foundation of China (H.G.), the startup research funding from China Agricultural University (H.G.), Chinese Universities Scientific Fund (Project Nos. 2011JS029 and 2011JS031) (H.G.), the National Scientific and Technology Supporting Program of China (2011BAE06B05-5) (H.G.), Nutriechem Company (H.G.), and the U.S. National Institutes of Health (NIH; O.K.: R01GM-071779 and P41GM081282). Computational facilitieswere funded by grants from ARO-DURIP and ONR-DURIP.
Funders:
Funding AgencyGrant Number
National Natural Science Foundation of ChinaUNSPECIFIED
China Agricultural UniversityUNSPECIFIED
Chinese Universities Scientific Fund2011JS029
Chinese Universities Scientific Fund2011JS031
National Scientific and Technology Supporting Program of China2011BAE06B05-5
Nutriechem CompanyUNSPECIFIED
NIHR01GM-071779
NIHP41GM081282
Army Research Office (ARO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
PubMed Central ID:PMC3163120
Record Number:CaltechAUTHORS:20111114-153026931
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20111114-153026931
Official Citation:Phosphine-Catalyzed Annulations of Azomethine Imines: Allene-Dependent [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] Pathways Risong Na, Chengfeng Jing, Qihai Xu, Hui Jiang, Xi Wu, Jiayan Shi, Jiangchun Zhong, Min Wang, Diego Benitez, Ekaterina Tkatchouk, William A. Goddard III, Hongchao Guo, and Ohyun Kwon Journal of the American Chemical Society 2011 133 (34), 13337-13348
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:27775
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:15 Nov 2011 15:48
Last Modified:27 Feb 2019 00:18

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