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Regio- and Stereoselective 1,2-Oxyhalogenation of Non-Conjugated Alkynes via Directed Nucleopalladation: Catalytic Access to Tetrasubstituted Alkenes.
Angew Chem Int Ed Engl. 2022 Oct 24; 61(43):e202209099.AC

Abstract

A catalytic 1,2-oxyhalogenation method that converts non-conjugated internal alkynes into tetrasubstituted alkenes with high regio- and stereoselectivity is described. Mechanistically, the reaction involves a PdII /PdIV catalytic cycle that begins with a directed oxypalladation step. The origin of regioselectivity is the preference for formation of a six-membered palladacycle intermediate, which is facilitated by an N,N-bidentate 2-(pyridin-2-yl)isopropyl (PIP) amide directing group. Selectivity for C(alkenyl)-X versus -N (X=halide) reductive elimination from the PdIV center depends on the identity of the halide anion; bromide and iodide engage in C(alkenyl)-X formation, while intramolecular C(alkenyl)-N reductive elimination occurs with chloride to furnish a lactam product. DFT calculations shed light on the origins of this phenomenon.

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Authors+Show Affiliations

Liu M
Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines Road, La Jolla, CA 92037, USA.
Sun J
Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines Road, La Jolla, CA 92037, USA.
Zhang T
Green Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou, Henan, 450001, P. R. China.
Ding Y
Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang, 310027, P. R. China.
Han YQ
Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang, 310027, P. R. China.
Martín-Montero R
Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines Road, La Jolla, CA 92037, USA.
Lan Y
Green Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou, Henan, 450001, P. R. China. School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing, 400030, P. R. China.
Shi BF
Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang, 310027, P. R. China.
Engle KM
Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines Road, La Jolla, CA 92037, USA.

MeSH

AlkenesAlkynesPalladiumBromidesIodidesChloridesLactamsAmides

Pub Type(s)

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

Language

eng

PubMed ID

36082442

Citation

Liu, Mingyu, et al. "Regio- and Stereoselective 1,2-Oxyhalogenation of Non-Conjugated Alkynes Via Directed Nucleopalladation: Catalytic Access to Tetrasubstituted Alkenes." Angewandte Chemie (International Ed. in English), vol. 61, no. 43, 2022, pp. e202209099.
Liu M, Sun J, Zhang T, et al. Regio- and Stereoselective 1,2-Oxyhalogenation of Non-Conjugated Alkynes via Directed Nucleopalladation: Catalytic Access to Tetrasubstituted Alkenes. Angew Chem Int Ed Engl. 2022;61(43):e202209099.
Liu, M., Sun, J., Zhang, T., Ding, Y., Han, Y. Q., Martín-Montero, R., Lan, Y., Shi, B. F., & Engle, K. M. (2022). Regio- and Stereoselective 1,2-Oxyhalogenation of Non-Conjugated Alkynes via Directed Nucleopalladation: Catalytic Access to Tetrasubstituted Alkenes. Angewandte Chemie (International Ed. in English), 61(43), e202209099. https://doi.org/10.1002/anie.202209099
Liu M, et al. Regio- and Stereoselective 1,2-Oxyhalogenation of Non-Conjugated Alkynes Via Directed Nucleopalladation: Catalytic Access to Tetrasubstituted Alkenes. Angew Chem Int Ed Engl. 2022 Oct 24;61(43):e202209099. PubMed PMID: 36082442.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Regio- and Stereoselective 1,2-Oxyhalogenation of Non-Conjugated Alkynes via Directed Nucleopalladation: Catalytic Access to Tetrasubstituted Alkenes. AU - Liu,Mingyu, AU - Sun,Juntao, AU - Zhang,Tao, AU - Ding,Yi, AU - Han,Ye-Qiang, AU - Martín-Montero,Raúl, AU - Lan,Yu, AU - Shi,Bing-Feng, AU - Engle,Keary M, Y1 - 2022/09/29/ PY - 2022/06/21/received PY - 2022/9/10/pubmed PY - 2022/10/21/medline PY - 2022/9/9/entrez KW - Alkene KW - Alkyne Functionalization KW - Directing Group KW - Oxyhalogenation KW - Palladium SP - e202209099 EP - e202209099 JF - Angewandte Chemie (International ed. in English) JO - Angew Chem Int Ed Engl VL - 61 IS - 43 N2 - A catalytic 1,2-oxyhalogenation method that converts non-conjugated internal alkynes into tetrasubstituted alkenes with high regio- and stereoselectivity is described. Mechanistically, the reaction involves a PdII /PdIV catalytic cycle that begins with a directed oxypalladation step. The origin of regioselectivity is the preference for formation of a six-membered palladacycle intermediate, which is facilitated by an N,N-bidentate 2-(pyridin-2-yl)isopropyl (PIP) amide directing group. Selectivity for C(alkenyl)-X versus -N (X=halide) reductive elimination from the PdIV center depends on the identity of the halide anion; bromide and iodide engage in C(alkenyl)-X formation, while intramolecular C(alkenyl)-N reductive elimination occurs with chloride to furnish a lactam product. DFT calculations shed light on the origins of this phenomenon. SN - 1521-3773 UR - https://www.unboundmedicine.com/medline/citation/36082442/Regio__and_Stereoselective_12_Oxyhalogenation_of_Non_Conjugated_Alkynes_via_Directed_Nucleopalladation:_Catalytic_Access_to_Tetrasubstituted_Alkenes_ DB - PRIME DP - Unbound Medicine ER -