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Weakly Nucleophilic Potassium Aryltrifluoroborates in Palladium-Catalyzed Suzuki–Miyaura Reactions: Relative Reactivity of K[4-RC6F4BF3] and the Role of Silver-Assistance in Acceleration of Transmetallation Full article

Journal Beilstein Journal of Organic Chemistry
ISSN: 1860-5397
Output data Year: 2015, Volume: 11, Pages: 608-616 Pages count : 9 DOI: 10.3762/bjoc.11.68
Tags Potassium polyfluoroaryltrifluoroborate, Silver(I) acceleration, Suzuki-Miyaura reaction
Authors Bardin V.V. 1,2 , Shabalin A.Y. 3 , Adonin N.Y. 2,3
Affiliations
1 N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, SB RAS, Acad. Lavrentjev Ave. 9, Novosibirsk, 630090, Russian Federation
2 Novosibirsk State University, Pirogova str., 2, Novosibirsk, 630090, Russian Federation
3 G.K. Boreskov Institute of Catalysis, SB RAS, Acad. Lavrentjev Ave. 5, Novosibirsk, 630090, Russian Federation

Abstract: Small differences in the reactivity of weakly nucleophilic potassium aryltrifluoroborates are revealed in the silver-assisted Pd-catalyzed cross-coupling of K[4-RC6F4BF3] (R = H, Bu, MeO, EtO, PrO, iPrO, BuO, t-BuO, CH2=CHCH2O, PhCH2O, PhCH2CH2O, PhO, F, pyrazol-1-yl, pyrrol-1-yl, and indol-1-yl) with ArX (4-BrC6H4CH3, 4-IC6H4F and 3-IC6H4F). An assumed role of silver(I) compounds AgmY (Y = O, NO3, SO4, BF4, F) consists in polarization of the Pd–X bond in neutral complex ArPdLnX with the generation of the related transition state or formation of [ArPdLn][XAgmY] with a highly electrophilic cation and subsequent transmetallation with the weakly nucleophilic borate. Efficiency of AgmY as a polarizing agent decreases in order Ag2O > AgNO3 ≈ Ag2SO4 > Ag[BF4] > AgF. No clear correlation between the reactivity of K[4-RC6F4BF3] and substituent electron parameters, σI and σR°, of the aryl group 4-RC6F4 was found.
Cite: Bardin V.V. , Shabalin A.Y. , Adonin N.Y.
Weakly Nucleophilic Potassium Aryltrifluoroborates in Palladium-Catalyzed Suzuki–Miyaura Reactions: Relative Reactivity of K[4-RC6F4BF3] and the Role of Silver-Assistance in Acceleration of Transmetallation
Beilstein Journal of Organic Chemistry. 2015. V.11. P.608-616. DOI: 10.3762/bjoc.11.68 WOS Scopus РИНЦ ANCAN PMID OpenAlex
Files: Full text from publisher
Dates:
Submitted: Jan 23, 2015
Accepted: Apr 9, 2015
Published print: May 4, 2015
Published online: May 4, 2015
Identifiers:
Web of science: WOS:000353874400001
Scopus: 2-s2.0-84930655108
Elibrary: 24045991
Chemical Abstracts: 2015:830447
Chemical Abstracts (print): 163:473794
PMID: 26124862
OpenAlex: W348623969
Citing:
DB Citing
Web of science 17
Scopus 17
Elibrary 17
OpenAlex 19
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