TY - JOUR
T1 - Rapid, Homogenous, B-Alkyl Suzuki-Miyaura Cross-Coupling of Boronic Esters
AU - Bock, Matthew J.
AU - Denmark, Scott E.
N1 - We are grateful to the National Institutes of Health (Grant GM R35 127010) for generous financial support. We thank the UIUC SCS support facilities (microanalysis, mass spectrometry, and NMR spectroscopy) for their assistance. Dr. Gerald Larson (Gelest) is thanked for generous gifts of TMSOK to support these studies. We also thank Wesley Wang (Prof. M. D. Burke) for providing samples of iPhos and CgMe-PPh(2,4-OMe). Vincent Kassel is acknowledged for conducting preliminary studies on the origin of protodehalogenation.
PY - 2024/11/15
Y1 - 2024/11/15
N2 - A rapid, anhydrous Suzuki-Miyaura cross-coupling of alkylboronic esters with aryl halides is described. Parallel experimentation revealed that the combination of AntPhos, an oxaphosphole ligand, neopentyldiol alkylboronic esters, and potassium trimethylsilanolate (TMSOK) enables successful cross-coupling. In general, reactions proceed in under 1 h with good yields and high linear/branched (l/b) selectivities. Crucially, two literature examples which previously took >20 h to reach completion were accomplished in a fraction of the time with the method described herein. Mechanistic studies revealed that the reaction proceeds through a stereoretentive pathway and identified the boronic ester skeleton as a predominant pathway for deleterious protodehalogenation.
AB - A rapid, anhydrous Suzuki-Miyaura cross-coupling of alkylboronic esters with aryl halides is described. Parallel experimentation revealed that the combination of AntPhos, an oxaphosphole ligand, neopentyldiol alkylboronic esters, and potassium trimethylsilanolate (TMSOK) enables successful cross-coupling. In general, reactions proceed in under 1 h with good yields and high linear/branched (l/b) selectivities. Crucially, two literature examples which previously took >20 h to reach completion were accomplished in a fraction of the time with the method described herein. Mechanistic studies revealed that the reaction proceeds through a stereoretentive pathway and identified the boronic ester skeleton as a predominant pathway for deleterious protodehalogenation.
UR - https://www.scopus.com/pages/publications/85187988195
UR - https://www.scopus.com/pages/publications/85187988195#tab=citedBy
U2 - 10.1021/acs.joc.4c00089
DO - 10.1021/acs.joc.4c00089
M3 - Article
C2 - 38483187
AN - SCOPUS:85187988195
SN - 0022-3263
VL - 89
SP - 16195
EP - 16202
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 22
ER -