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Rhodium-catalyzed cycloisomerization of 1,6-enynes with an intramolecular halogen shift: reaction scope and mechanism.
J Am Chem Soc. 2004 Jun 23; 126(24):7601-7.JA

Abstract

The rhodium(I)-species-catalyzed cycloisomerization reaction of a wide spectrum of 1,6-enynes with an unusual intramolecular halogen shift was investigated. This Rh-catalyzed enyne cyclization reaction represents a new process for the synthesis of stereodefined alpha-halomethylene-gamma-butyrolactones, lactams, tetrahydrofurans, pyrrolidines, and cyclopentanes. Coordinatively unsaturated rhodium species ([Rh(COD)Cl](2) + dppb + AgSbF(6)) only catalyzes the reaction with enyne substrates bearing a Z-form double bond, while neutral rhodium species (RhCl(PPh(3))(3)) could catalyze enyne substrates bearing a Z- or E-form double bond to form the desired products and has a wider substrate scopes. The mechanism of the reaction was studied by the employment of control experiments with different enyne isomers, and a pi-allyl rhodium intermediate was suggested to explain the formation of the cyclic products with an intramolecular halogen shift.

Authors+Show Affiliations

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, China.No affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

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

Language

eng

PubMed ID

15198608

Citation

Tong, Xiaofeng, et al. "Rhodium-catalyzed Cycloisomerization of 1,6-enynes With an Intramolecular Halogen Shift: Reaction Scope and Mechanism." Journal of the American Chemical Society, vol. 126, no. 24, 2004, pp. 7601-7.
Tong X, Li D, Zhang Z, et al. Rhodium-catalyzed cycloisomerization of 1,6-enynes with an intramolecular halogen shift: reaction scope and mechanism. J Am Chem Soc. 2004;126(24):7601-7.
Tong, X., Li, D., Zhang, Z., & Zhang, X. (2004). Rhodium-catalyzed cycloisomerization of 1,6-enynes with an intramolecular halogen shift: reaction scope and mechanism. Journal of the American Chemical Society, 126(24), 7601-7.
Tong X, et al. Rhodium-catalyzed Cycloisomerization of 1,6-enynes With an Intramolecular Halogen Shift: Reaction Scope and Mechanism. J Am Chem Soc. 2004 Jun 23;126(24):7601-7. PubMed PMID: 15198608.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Rhodium-catalyzed cycloisomerization of 1,6-enynes with an intramolecular halogen shift: reaction scope and mechanism. AU - Tong,Xiaofeng, AU - Li,Dao, AU - Zhang,Zhaoguo, AU - Zhang,Xumu, PY - 2004/6/17/pubmed PY - 2004/10/13/medline PY - 2004/6/17/entrez SP - 7601 EP - 7 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 126 IS - 24 N2 - The rhodium(I)-species-catalyzed cycloisomerization reaction of a wide spectrum of 1,6-enynes with an unusual intramolecular halogen shift was investigated. This Rh-catalyzed enyne cyclization reaction represents a new process for the synthesis of stereodefined alpha-halomethylene-gamma-butyrolactones, lactams, tetrahydrofurans, pyrrolidines, and cyclopentanes. Coordinatively unsaturated rhodium species ([Rh(COD)Cl](2) + dppb + AgSbF(6)) only catalyzes the reaction with enyne substrates bearing a Z-form double bond, while neutral rhodium species (RhCl(PPh(3))(3)) could catalyze enyne substrates bearing a Z- or E-form double bond to form the desired products and has a wider substrate scopes. The mechanism of the reaction was studied by the employment of control experiments with different enyne isomers, and a pi-allyl rhodium intermediate was suggested to explain the formation of the cyclic products with an intramolecular halogen shift. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/15198608/Rhodium_catalyzed_cycloisomerization_of_16_enynes_with_an_intramolecular_halogen_shift:_reaction_scope_and_mechanism_ L2 - https://doi.org/10.1021/ja0498639 DB - PRIME DP - Unbound Medicine ER -