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Rh-catalyzed (5+2) cycloadditions of 3-acyloxy-1,4-enynes and alkynes: computational study of mechanism, reactivity, and regioselectivity.
J Am Chem Soc. 2013 Jun 26; 135(25):9271-4.JA

Abstract

The mechanism of Rh-catalyzed (5+2) cycloadditions of 3-acyloxy-1,4-enyne (ACE) and alkynes is investigated using density functional theory calculations. The catalytic cycle involves 1,2-acyloxy migration, alkyne insertion, and reductive elimination to form the cycloheptatriene product. In contrast to the (5+2) cycloadditions with vinylcyclopropanes (VCPs), in which alkyne inserts into a rhodium-allyl bond, alkyne insertion into a Rh-C(sp(2)) bond is preferred. The 1,2-acyloxy migration is found to be the rate-determining step of the catalytic cycle. The electron-rich p-dimethylaminobenzoate substrate promotes 1,2-acyloxy migration and significantly increases the reactivity. In the regioselectivity-determining alkyne insertion step, the alkyne substituent prefers to be distal to the forming C-C bond and thus distal to the OAc group in the product.

Authors+Show Affiliations

Department of Chemistry, Nankai University, Tianjin, 300071, PR China. xxfang@nankai.edu.cnNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

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

Language

eng

PubMed ID

23725341

Citation

Xu, Xiufang, et al. "Rh-catalyzed (5+2) Cycloadditions of 3-acyloxy-1,4-enynes and Alkynes: Computational Study of Mechanism, Reactivity, and Regioselectivity." Journal of the American Chemical Society, vol. 135, no. 25, 2013, pp. 9271-4.
Xu X, Liu P, Shu XZ, et al. Rh-catalyzed (5+2) cycloadditions of 3-acyloxy-1,4-enynes and alkynes: computational study of mechanism, reactivity, and regioselectivity. J Am Chem Soc. 2013;135(25):9271-4.
Xu, X., Liu, P., Shu, X. Z., Tang, W., & Houk, K. N. (2013). Rh-catalyzed (5+2) cycloadditions of 3-acyloxy-1,4-enynes and alkynes: computational study of mechanism, reactivity, and regioselectivity. Journal of the American Chemical Society, 135(25), 9271-4. https://doi.org/10.1021/ja4036785
Xu X, et al. Rh-catalyzed (5+2) Cycloadditions of 3-acyloxy-1,4-enynes and Alkynes: Computational Study of Mechanism, Reactivity, and Regioselectivity. J Am Chem Soc. 2013 Jun 26;135(25):9271-4. PubMed PMID: 23725341.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Rh-catalyzed (5+2) cycloadditions of 3-acyloxy-1,4-enynes and alkynes: computational study of mechanism, reactivity, and regioselectivity. AU - Xu,Xiufang, AU - Liu,Peng, AU - Shu,Xing-zhong, AU - Tang,Weiping, AU - Houk,K N, Y1 - 2013/06/14/ PY - 2013/6/4/entrez PY - 2013/6/4/pubmed PY - 2014/1/15/medline SP - 9271 EP - 4 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 135 IS - 25 N2 - The mechanism of Rh-catalyzed (5+2) cycloadditions of 3-acyloxy-1,4-enyne (ACE) and alkynes is investigated using density functional theory calculations. The catalytic cycle involves 1,2-acyloxy migration, alkyne insertion, and reductive elimination to form the cycloheptatriene product. In contrast to the (5+2) cycloadditions with vinylcyclopropanes (VCPs), in which alkyne inserts into a rhodium-allyl bond, alkyne insertion into a Rh-C(sp(2)) bond is preferred. The 1,2-acyloxy migration is found to be the rate-determining step of the catalytic cycle. The electron-rich p-dimethylaminobenzoate substrate promotes 1,2-acyloxy migration and significantly increases the reactivity. In the regioselectivity-determining alkyne insertion step, the alkyne substituent prefers to be distal to the forming C-C bond and thus distal to the OAc group in the product. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/23725341/Rh_catalyzed__5+2__cycloadditions_of_3_acyloxy_14_enynes_and_alkynes:_computational_study_of_mechanism_reactivity_and_regioselectivity_ L2 - https://doi.org/10.1021/ja4036785 DB - PRIME DP - Unbound Medicine ER -