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Enantioselective reductive cyclization of 1,6-enynes via rhodium-catalyzed asymmetric hydrogenation: C-C bond formation precedes hydrogen activation.
J Am Chem Soc. 2005 May 04; 127(17):6174-5.JA

Abstract

Asymmetric hydrogenation of 1,6-enynes using chirally modified cationic rhodium precatalysts enables enantioselective reductive cyclization to afford alkylidene-substituted carbocycles and heterocycles in a completely atom economical fashion. Good to excellent yields and exceptional levels of asymmetric induction are observed across a structurally diverse set of substrates. Mechanistic studies involving hydrogen-deuterium crossover experiments, along with the observance of nonconjugated cycloisomerization products 14c and 15c, suggest rhodium(III) metallocyclopentene formation occurs in advance of hydrogen activation. This oxidative coupling-hydrogenolytic cleavage motif should play a key role in the design of related hydrogen-mediated couplings.

Authors+Show Affiliations

Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712, USA.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

15853314

Citation

Jang, Hye-Young, et al. "Enantioselective Reductive Cyclization of 1,6-enynes Via Rhodium-catalyzed Asymmetric Hydrogenation: C-C Bond Formation Precedes Hydrogen Activation." Journal of the American Chemical Society, vol. 127, no. 17, 2005, pp. 6174-5.
Jang HY, Hughes FW, Gong H, et al. Enantioselective reductive cyclization of 1,6-enynes via rhodium-catalyzed asymmetric hydrogenation: C-C bond formation precedes hydrogen activation. J Am Chem Soc. 2005;127(17):6174-5.
Jang, H. Y., Hughes, F. W., Gong, H., Zhang, J., Brodbelt, J. S., & Krische, M. J. (2005). Enantioselective reductive cyclization of 1,6-enynes via rhodium-catalyzed asymmetric hydrogenation: C-C bond formation precedes hydrogen activation. Journal of the American Chemical Society, 127(17), 6174-5.
Jang HY, et al. Enantioselective Reductive Cyclization of 1,6-enynes Via Rhodium-catalyzed Asymmetric Hydrogenation: C-C Bond Formation Precedes Hydrogen Activation. J Am Chem Soc. 2005 May 4;127(17):6174-5. PubMed PMID: 15853314.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Enantioselective reductive cyclization of 1,6-enynes via rhodium-catalyzed asymmetric hydrogenation: C-C bond formation precedes hydrogen activation. AU - Jang,Hye-Young, AU - Hughes,Freddie W, AU - Gong,Hegui, AU - Zhang,Junmei, AU - Brodbelt,Jennifer S, AU - Krische,Michael J, PY - 2005/4/28/pubmed PY - 2005/4/28/medline PY - 2005/4/28/entrez SP - 6174 EP - 5 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 127 IS - 17 N2 - Asymmetric hydrogenation of 1,6-enynes using chirally modified cationic rhodium precatalysts enables enantioselective reductive cyclization to afford alkylidene-substituted carbocycles and heterocycles in a completely atom economical fashion. Good to excellent yields and exceptional levels of asymmetric induction are observed across a structurally diverse set of substrates. Mechanistic studies involving hydrogen-deuterium crossover experiments, along with the observance of nonconjugated cycloisomerization products 14c and 15c, suggest rhodium(III) metallocyclopentene formation occurs in advance of hydrogen activation. This oxidative coupling-hydrogenolytic cleavage motif should play a key role in the design of related hydrogen-mediated couplings. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/15853314/Enantioselective_reductive_cyclization_of_16_enynes_via_rhodium_catalyzed_asymmetric_hydrogenation:_C_C_bond_formation_precedes_hydrogen_activation_ L2 - https://doi.org/10.1021/ja042645v DB - PRIME DP - Unbound Medicine ER -
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