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Rh(II)-Catalyzed skeletal reorganization of 1,6- and 1,7-enynes through electrophilic activation of alkynes.
J Am Chem Soc. 2009 Oct 28; 131(42):15203-11.JA

Abstract

The skeletal reorganization of 1,6- and 1,7-enynes leading to 1-vinylcycloalkenes using Rh(II) as a catalyst is reported. Two possible isomers of 1-vinylcycloalkenes, type I and type II, can be obtained, the ratio of which are highly dependent on the substitution pattern of the enynes used. Formation of type I compounds involves a single cleavage of a C-C double bond, the product of which is identical to that of enyne metathesis. In contrast, the formation of type II compounds involves the double cleavage of both the C-C double and triple bonds, which has an anomalous bond connection. The presence of both a phenyl group at the alkyne carbon and a methyl group at the internal alkene carbon facilitates the formation of type II compounds. The electronic and steric nature of the substituents on the aromatic ring also affects the ratio of type I and type II. The nature of a tether also has a significant effect on the course of the reaction. Experimental evidence for the intermediacy of a cyclopropyl rhodium carbenoid, a key intermediate in the skeletal reorganization of enynes, is also reported. In addition to the skeletal reorganization of enynes, Rh(II) complexes were found to have a high catalytic activity for some cycloisomerization reactions of alkyne derivatives, including the bicyclization of enynes to bicyclo[4.1.0]heptene derivatives and the cyclization of alkynylfurans to phenol derivatives.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Ota K
Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan.
Lee SI
No affiliation info available
Tang JM
No affiliation info available
Takachi M
No affiliation info available
Nakai H
No affiliation info available
Morimoto T
No affiliation info available
Sakurai H
No affiliation info available
Kataoka K
No affiliation info available
Chatani N
No affiliation info available

MeSH

AlkynesCatalysisCyclizationElectronsIsomerismMolecular StructureRhodium

Pub Type(s)

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

Language

eng

PubMed ID

19807073

Citation

Ota, Kazusa, et al. "Rh(II)-Catalyzed Skeletal Reorganization of 1,6- and 1,7-enynes Through Electrophilic Activation of Alkynes." Journal of the American Chemical Society, vol. 131, no. 42, 2009, pp. 15203-11.
Ota K, Lee SI, Tang JM, et al. Rh(II)-Catalyzed skeletal reorganization of 1,6- and 1,7-enynes through electrophilic activation of alkynes. J Am Chem Soc. 2009;131(42):15203-11.
Ota, K., Lee, S. I., Tang, J. M., Takachi, M., Nakai, H., Morimoto, T., Sakurai, H., Kataoka, K., & Chatani, N. (2009). Rh(II)-Catalyzed skeletal reorganization of 1,6- and 1,7-enynes through electrophilic activation of alkynes. Journal of the American Chemical Society, 131(42), 15203-11. https://doi.org/10.1021/ja9047637
Ota K, et al. Rh(II)-Catalyzed Skeletal Reorganization of 1,6- and 1,7-enynes Through Electrophilic Activation of Alkynes. J Am Chem Soc. 2009 Oct 28;131(42):15203-11. PubMed PMID: 19807073.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Rh(II)-Catalyzed skeletal reorganization of 1,6- and 1,7-enynes through electrophilic activation of alkynes. AU - Ota,Kazusa, AU - Lee,Sang Ick, AU - Tang,Jhih-Meng, AU - Takachi,Manabu, AU - Nakai,Hiromi, AU - Morimoto,Tsumoru, AU - Sakurai,Hitoshi, AU - Kataoka,Ken, AU - Chatani,Naoto, PY - 2009/10/8/entrez PY - 2009/10/8/pubmed PY - 2010/2/19/medline SP - 15203 EP - 11 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 131 IS - 42 N2 - The skeletal reorganization of 1,6- and 1,7-enynes leading to 1-vinylcycloalkenes using Rh(II) as a catalyst is reported. Two possible isomers of 1-vinylcycloalkenes, type I and type II, can be obtained, the ratio of which are highly dependent on the substitution pattern of the enynes used. Formation of type I compounds involves a single cleavage of a C-C double bond, the product of which is identical to that of enyne metathesis. In contrast, the formation of type II compounds involves the double cleavage of both the C-C double and triple bonds, which has an anomalous bond connection. The presence of both a phenyl group at the alkyne carbon and a methyl group at the internal alkene carbon facilitates the formation of type II compounds. The electronic and steric nature of the substituents on the aromatic ring also affects the ratio of type I and type II. The nature of a tether also has a significant effect on the course of the reaction. Experimental evidence for the intermediacy of a cyclopropyl rhodium carbenoid, a key intermediate in the skeletal reorganization of enynes, is also reported. In addition to the skeletal reorganization of enynes, Rh(II) complexes were found to have a high catalytic activity for some cycloisomerization reactions of alkyne derivatives, including the bicyclization of enynes to bicyclo[4.1.0]heptene derivatives and the cyclization of alkynylfurans to phenol derivatives. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/19807073/Rh_II__Catalyzed_skeletal_reorganization_of_16__and_17_enynes_through_electrophilic_activation_of_alkynes_ L2 - https://doi.org/10.1021/ja9047637 DB - PRIME DP - Unbound Medicine ER -