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Nickel-catalyzed Mizoroki-Heck reaction of aryl sulfonates and chlorides with electronically unbiased terminal olefins: high selectivity for branched products.
Angew Chem Int Ed Engl 2014; 53(7):1858-61AC

Abstract

Achieving high selectivity in the Heck reaction of electronically unbiased alkenes has been a longstanding challenge. Using a nickel-catalyzed cationic Heck reaction, we were able to achieve excellent selectivity for branched products (≥19:1 in all cases) over a wide range of aryl electrophiles and aliphatic olefins. A bidentate ligand with a suitable bite angle and steric profile was key to obtaining high branched/linear selectivity, whereas the appropriate base suppressed alkene isomerization of the product. Although aryl triflates are traditionally used to access the cationic Heck pathway, we have shown that, by using triethylsilyl trifluoromethanesulfonate, we can effect a counterion exchange of the catalytic nickel complex, such that cheaper and more stable aryl chlorides, mesylates, tosylates, and sulfamates can be used to yield the same branched products with high selectivity.

Authors+Show Affiliations

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139 (USA) http://web.mit.edu/chemistry/jamison.No affiliation info availableNo affiliation info available

Pub Type(s)

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

Language

eng

PubMed ID

24402966

Citation

Tasker, Sarah Z., et al. "Nickel-catalyzed Mizoroki-Heck Reaction of Aryl Sulfonates and Chlorides With Electronically Unbiased Terminal Olefins: High Selectivity for Branched Products." Angewandte Chemie (International Ed. in English), vol. 53, no. 7, 2014, pp. 1858-61.
Tasker SZ, Gutierrez AC, Jamison TF. Nickel-catalyzed Mizoroki-Heck reaction of aryl sulfonates and chlorides with electronically unbiased terminal olefins: high selectivity for branched products. Angew Chem Int Ed Engl. 2014;53(7):1858-61.
Tasker, S. Z., Gutierrez, A. C., & Jamison, T. F. (2014). Nickel-catalyzed Mizoroki-Heck reaction of aryl sulfonates and chlorides with electronically unbiased terminal olefins: high selectivity for branched products. Angewandte Chemie (International Ed. in English), 53(7), pp. 1858-61. doi:10.1002/anie.201308391.
Tasker SZ, Gutierrez AC, Jamison TF. Nickel-catalyzed Mizoroki-Heck Reaction of Aryl Sulfonates and Chlorides With Electronically Unbiased Terminal Olefins: High Selectivity for Branched Products. Angew Chem Int Ed Engl. 2014 Feb 10;53(7):1858-61. PubMed PMID: 24402966.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Nickel-catalyzed Mizoroki-Heck reaction of aryl sulfonates and chlorides with electronically unbiased terminal olefins: high selectivity for branched products. AU - Tasker,Sarah Z, AU - Gutierrez,Alicia C, AU - Jamison,Timothy F, Y1 - 2014/01/08/ PY - 2013/09/25/received PY - 2013/11/19/revised PY - 2014/1/10/entrez PY - 2014/1/10/pubmed PY - 2014/10/1/medline KW - Heck reaction KW - alkenes KW - nickel KW - regioselectivity SP - 1858 EP - 61 JF - Angewandte Chemie (International ed. in English) JO - Angew. Chem. Int. Ed. Engl. VL - 53 IS - 7 N2 - Achieving high selectivity in the Heck reaction of electronically unbiased alkenes has been a longstanding challenge. Using a nickel-catalyzed cationic Heck reaction, we were able to achieve excellent selectivity for branched products (≥19:1 in all cases) over a wide range of aryl electrophiles and aliphatic olefins. A bidentate ligand with a suitable bite angle and steric profile was key to obtaining high branched/linear selectivity, whereas the appropriate base suppressed alkene isomerization of the product. Although aryl triflates are traditionally used to access the cationic Heck pathway, we have shown that, by using triethylsilyl trifluoromethanesulfonate, we can effect a counterion exchange of the catalytic nickel complex, such that cheaper and more stable aryl chlorides, mesylates, tosylates, and sulfamates can be used to yield the same branched products with high selectivity. SN - 1521-3773 UR - https://www.unboundmedicine.com/medline/citation/24402966/Nickel_catalyzed_Mizoroki_Heck_reaction_of_aryl_sulfonates_and_chlorides_with_electronically_unbiased_terminal_olefins:_high_selectivity_for_branched_products_ L2 - https://doi.org/10.1002/anie.201308391 DB - PRIME DP - Unbound Medicine ER -