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Highly enantioselective reductive cyclization of acetylenic aldehydes via rhodium catalyzed asymmetric hydrogenation.
J Am Chem Soc. 2006 Aug 23; 128(33):10674-5.JA

Abstract

Catalytic hydrogenation of acetylenic aldehydes 1a-12a using chirally modified cationic rhodium catalysts enables highly enantioselective reductive cyclization to afford cyclic allylic alcohols 1b-12b. Using an achiral hydrogenation catalyst, the chiral racemic acetylenic aldehydes 13a-15a engage in highly syn-diastereoselective reductive cyclizations to afford cyclic allylic alcohols 13b-15b. Ozonolysis of cyclization products 7b and 9b allows access to optically enriched alpha-hydroxy ketones 7c and 9c. Reductive cyclization of enyne 7a under a deuterium atmosphere provides the monodeuterated product deuterio-7b, consistent with a catalytic mechanism involving alkyne-carbonyl oxidative coupling followed by hydrogenolytic cleavage of the resulting oxametallacycle. These hydrogen-mediated transformations represent the first examples of the enantioselective reductive cyclization of acetylenic aldehydes.

Authors+Show Affiliations

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

Pub Type(s)

Journal Article
Research Support, N.I.H., Extramural
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

16910650

Citation

Rhee, Jong Uk, and Michael J. Krische. "Highly Enantioselective Reductive Cyclization of Acetylenic Aldehydes Via Rhodium Catalyzed Asymmetric Hydrogenation." Journal of the American Chemical Society, vol. 128, no. 33, 2006, pp. 10674-5.
Rhee JU, Krische MJ. Highly enantioselective reductive cyclization of acetylenic aldehydes via rhodium catalyzed asymmetric hydrogenation. J Am Chem Soc. 2006;128(33):10674-5.
Rhee, J. U., & Krische, M. J. (2006). Highly enantioselective reductive cyclization of acetylenic aldehydes via rhodium catalyzed asymmetric hydrogenation. Journal of the American Chemical Society, 128(33), 10674-5.
Rhee JU, Krische MJ. Highly Enantioselective Reductive Cyclization of Acetylenic Aldehydes Via Rhodium Catalyzed Asymmetric Hydrogenation. J Am Chem Soc. 2006 Aug 23;128(33):10674-5. PubMed PMID: 16910650.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Highly enantioselective reductive cyclization of acetylenic aldehydes via rhodium catalyzed asymmetric hydrogenation. AU - Rhee,Jong Uk, AU - Krische,Michael J, PY - 2006/8/17/pubmed PY - 2007/8/19/medline PY - 2006/8/17/entrez SP - 10674 EP - 5 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 128 IS - 33 N2 - Catalytic hydrogenation of acetylenic aldehydes 1a-12a using chirally modified cationic rhodium catalysts enables highly enantioselective reductive cyclization to afford cyclic allylic alcohols 1b-12b. Using an achiral hydrogenation catalyst, the chiral racemic acetylenic aldehydes 13a-15a engage in highly syn-diastereoselective reductive cyclizations to afford cyclic allylic alcohols 13b-15b. Ozonolysis of cyclization products 7b and 9b allows access to optically enriched alpha-hydroxy ketones 7c and 9c. Reductive cyclization of enyne 7a under a deuterium atmosphere provides the monodeuterated product deuterio-7b, consistent with a catalytic mechanism involving alkyne-carbonyl oxidative coupling followed by hydrogenolytic cleavage of the resulting oxametallacycle. These hydrogen-mediated transformations represent the first examples of the enantioselective reductive cyclization of acetylenic aldehydes. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/16910650/Highly_enantioselective_reductive_cyclization_of_acetylenic_aldehydes_via_rhodium_catalyzed_asymmetric_hydrogenation_ L2 - https://doi.org/10.1021/ja0637954 DB - PRIME DP - Unbound Medicine ER -
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