Pd-catalyzed C-H functionalisation affords effective synthetic tools to construct C-C and C-X bonds. Despite the challenges, the distal functionalization of C(sp)-H bonds has witnessed significant developments and the use of bidentate auxiliaries has garnished this area by providing an opportunity to control reactivity as well as selectivity beyond proximal sites. This article covers the recent developments on the Pd-catalyzed bidentate auxiliary-assisted distal C(sp)-H functionalization and is categorized based on the nature of functionalizations.
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http://dx.doi.org/10.1039/d1cc05291h | DOI Listing |
Chemistry
December 2024
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, China.
Pd-catalyzed alkoxycarbonylation of internal alkynes provides a straightforward access to α,β-disubstituted acrylic esters. Compared with the well-established regioselective alkoxycarbonylation of terminal alkynes, the regioselective hydrocarboxylation of non-functionalized unsymmetric internal alkynes was more challenging owing to the delicate differences of properties between the two substituents. Herein, by using either monophosphine ligand based on 2,3-dihydrobenzo[d][1,3]oxaphosphole motif or bidentate ligand Ph-Phox, the regioselective alkoxycarbonylations of aryl-aryl, aryl-alkyl and alkyl-alkyl disubstituted alkynes were achieved, giving a diversity of trisubstituted α,β-unsaturated carboxylic esters with moderate to excellent yields and high regioselectivity.
View Article and Find Full Text PDFMolecules
November 2024
State Key Laboratory of Functions and Applications of Medicinal Plants, Guizhou Medical University, 3491 Gaohai Road, Guiyang 550014, China.
Org Lett
August 2024
MOE Key Laboratory of Cluster Science, Beijing Key Laboratory of Photoelectronic-Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, P. R. China.
Using l-methionine (Met) as the endogenous directing group, we developed Pd-catalyzed β-C(sp)-H glycosylation of peptides with 1-iodoglycals. A wide range of tri- to hexapeptides containing the Ala-Met motifs underwent Ala C-H glycosylation under the standard conditions to give the glycopeptides smoothly. 15 proteinogenic amino acids (with easily removable protecting groups) were well tolerated.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA.
Pd(II)-catalyzed enantioselective C-H activation has emerged as a versatile platform for constructing point, axial, and planar chirality. Herein, we present an unexpected discovery of a Pd-catalyzed enantioselective cascade β,γ-methylene C(sp)-H diarylation of free carboxylic acids using bidentate chiral mono-protected amino thioether ligands (MPAThio), enabling one-step synthesis of a complex chiral 9,10-dihydrophenanthrene scaffolds with high enantioselectivity. In this process, two methylene C(sp)-H bonds and three C(sp)-H bonds were activated, leading to the formation of four C-C bonds and three chiral centers in one pot.
View Article and Find Full Text PDFOrg Lett
January 2024
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China.
8-Aminoquinoline (AQ) has proven to be a highly effective bidentate directing group for palladium-catalyzed C-H functionalization reactions. However, enantiocontrol of AQ-directed C(sp)-H functionalization reactions has been challenging. Herein, a new protocol is presented for the Pd-catalyzed enantioselective arylation of unactivated β C(sp)-H bonds of alkyl carboxamides with aryl iodides using a C-iodinated 8-aminoquinolines (IQ) auxiliary in conjugation with a BINOL ligand.
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