skip to main content


Title: Sulfones as Synthetic Linchpins: Transition-Metal-Free sp 3 -sp 2 and sp 2 -sp 2 Cross-Couplings Between Geminal Bis(sulfones) and Organolithium Compounds
NSF-PAR ID:
10059550
Author(s) / Creator(s):
 ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Chemistry - A European Journal
Volume:
24
Issue:
36
ISSN:
0947-6539
Page Range / eLocation ID:
9066 to 9074
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    The first cobalt‐catalyzed cross‐coupling of aryl tosylates with alkyl and aryl Grignard reagents is reported. The catalytic system uses CoF3and NHCs (NHC=N‐heterocyclic carbene) as ancillary ligands. The reaction proceeds via highly selective C−O bond functionalization, leading to the corresponding products in up to 98 % yield. The employment of alkyl Grignard reagents allows to achieve a rare C(sp2)−C(sp3) cross‐coupling of C−O electrophiles, circumventing isomerization and β‐hydride elimination problems. The use of aryl Grignards leads to the formation of biaryls. The C−O cross‐coupling sets the stage for a sequential cross‐coupling by exploiting the orthogonal selectivity of the catalytic system.

     
    more » « less
  2. Although iron catalyzed cross-coupling reactions show extraordinary promise in reducing the environmental impact of more toxic and scarce transition metals, one of the main challenges is the use of reprotoxic NMP (NMP = N -methylpyrrolidone) as the key ligand to iron in the most successful protocols in this reactivity platform. Herein, we report that non-toxic and sustainable N -butylpyrrolidone (NBP) serves as a highly effective substitute for NMP in iron-catalyzed C(sp 2 )–C(sp 3 ) cross-coupling of aryl chlorides with alkyl Grignard reagents. This challenging alkylation proceeds with organometallics bearing β-hydrogens with efficiency superseding or matching that of NMP with ample scope and broad functional group tolerance. Appealing applications are demonstrated in the cross-coupling in the presence of sensitive functional groups and the synthesis of several pharmaceutical intermediates, including a dual NK1/serotonin inhibitor, a fibrinolysis inhibitor and an antifungal agent. Considering that the iron/NMP system has emerged as one of the most powerful iron cross-coupling technologies available in both academic and industrial research, we anticipate that this method will be of broad interest. 
    more » « less