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 | Sciact - CRIS-system of Boreskov Institute of Catalysis

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

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.

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

Full text from publisher

Submitted:	Jan 23, 2015
Accepted:	Apr 9, 2015
Published print:	May 4, 2015
Published online:	May 4, 2015

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

DB	Citing
Web of science	17
Scopus	17
Elibrary	16
OpenAlex	17