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The mechanistic puzzle of transition-metal-catalyzed skeletal rearrangements of enynes.
Chemistry. 2006 Aug 07; 12(23):5916-23.C

Abstract

Three pathways actually compete in metal-catalyzed cyclizations of enynes in which the metal selectively activates the alkyne: an endocyclic process and two exo-cyclizations, one proceeding by anti attack of the alkene and a second one resulting in a syn addition. Although cyclobutenes may be formed in transition-metal-catalyzed cyclization of some enynes, particularly, 1,7-enynes, these compounds are not necessarily the intermediates in the skeletal rearrangement. Cyclobutenes are formed by ring expansion of syn-cyclopropyl metal-carbenes formed in the syn pathway.

Authors+Show Affiliations

Nieto-Oberhuber C
Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona, Spain.
López S
No affiliation info available
Jiménez-Núñez E
No affiliation info available
Echavarren AM
No affiliation info available

MeSH

AlkenesAlkynesCatalysisCyclizationMolecular ConformationStereoisomerismTransition Elements

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

16755620

Citation

Nieto-Oberhuber, Cristina, et al. "The Mechanistic Puzzle of Transition-metal-catalyzed Skeletal Rearrangements of Enynes." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 12, no. 23, 2006, pp. 5916-23.
Nieto-Oberhuber C, López S, Jiménez-Núñez E, et al. The mechanistic puzzle of transition-metal-catalyzed skeletal rearrangements of enynes. Chemistry. 2006;12(23):5916-23.
Nieto-Oberhuber, C., López, S., Jiménez-Núñez, E., & Echavarren, A. M. (2006). The mechanistic puzzle of transition-metal-catalyzed skeletal rearrangements of enynes. Chemistry (Weinheim an Der Bergstrasse, Germany), 12(23), 5916-23.
Nieto-Oberhuber C, et al. The Mechanistic Puzzle of Transition-metal-catalyzed Skeletal Rearrangements of Enynes. Chemistry. 2006 Aug 7;12(23):5916-23. PubMed PMID: 16755620.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - The mechanistic puzzle of transition-metal-catalyzed skeletal rearrangements of enynes. AU - Nieto-Oberhuber,Cristina, AU - López,Salomé, AU - Jiménez-Núñez,Eloísa, AU - Echavarren,Antonio M, PY - 2006/6/7/pubmed PY - 2007/1/31/medline PY - 2006/6/7/entrez SP - 5916 EP - 23 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 12 IS - 23 N2 - Three pathways actually compete in metal-catalyzed cyclizations of enynes in which the metal selectively activates the alkyne: an endocyclic process and two exo-cyclizations, one proceeding by anti attack of the alkene and a second one resulting in a syn addition. Although cyclobutenes may be formed in transition-metal-catalyzed cyclization of some enynes, particularly, 1,7-enynes, these compounds are not necessarily the intermediates in the skeletal rearrangement. Cyclobutenes are formed by ring expansion of syn-cyclopropyl metal-carbenes formed in the syn pathway. SN - 0947-6539 UR - https://www.unboundmedicine.com/medline/citation/16755620/The_mechanistic_puzzle_of_transition_metal_catalyzed_skeletal_rearrangements_of_enynes_ DB - PRIME DP - Unbound Medicine ER -