We have studied copper-catalyzed cross-coupling of chiral α-CF-substituted allylboronic acids with α-diazoketones. The reaction proceeds with excellent regioselectivity and stereoselectivity via allylic rearrangement. The method is useful for formation a new allylic C(sp)-C(sp) bond with high selectivity. The poor yield is a limitation of this reaction.
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http://dx.doi.org/10.1021/acs.joc.4c02869 | DOI Listing |
J Org Chem
January 2025
Department of Organic Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden.
We have studied copper-catalyzed cross-coupling of chiral α-CF-substituted allylboronic acids with α-diazoketones. The reaction proceeds with excellent regioselectivity and stereoselectivity via allylic rearrangement. The method is useful for formation a new allylic C(sp)-C(sp) bond with high selectivity.
View Article and Find Full Text PDFJ Org Chem
January 2025
College of Chemistry and Chemical Engineering, Green Catalysis & Synthesis Key Laboratory of Xinyang City, Xinyang Normal University, Xinyang 464000, China.
A novel and efficient method for the intermolecular hydroxysulfonylation of vinylarenes using sodium sulfinates has been achieved through aerobic copper catalysis. This transformation proceeded smoothly with green air as the terminal oxidant in the presence of Cu (I)/1,10-phenanthroline as an efficient catalytic system, leading to an array of β-hydroxysulfones in moderate to high yields. The significant advantages of this protocol are the mild reaction conditions, readily available starting materials, good functional-group compatibility, synthetic convenience, and practicability.
View Article and Find Full Text PDFOrg Lett
January 2025
Graduate School of Life Sciences, Tohoku University, 2-1-1 Katahira, 980-8577 Aoba-ku, Sendai, Japan.
Our efforts toward the synthesis of the marine natural product portimine are described. The key to the synthesis of the skeleton is a stereoretentive copper-catalyzed C()-C() Stille-type cross-coupling that enables the convergent assembly of functionalized fragments. The core skeleton of portimine was constructed via ring-closing metathesis and transannular acetal formation.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, Stockholm, SE-10691, Sweden.
Herein, we present a highly efficient allylic substitution of carbonates with Grignard reagents using a reusable cellulose-supported nanocopper catalyst. This approach highlights the first instance of heterogeneous catalysis for the cross-coupling of allylic alcohol substrates with Grignard reagents. The method features high yields, excellent regioselectivity, and complete chirality transfer.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Inorganic Materials and Catalysis Division, CSIR-Central Salt and Marine Chemicals Research Institute, G.B. Marg, Bhavnagar 364002, Gujarat, India.
Arylacetic acid equivalents bearing a pyridine group undergo C(sp)-H/C(sp)-H cross coupling with diverse methylarenes in the presence of a copper based catalyst system. The reaction proceeds the formation of α-carbonyl radicals giving access to α,β-diarylpropionic acids. Preliminary study suggests that the catalyst system is capable of transforming arylbenzyl ketones into 1,2,3-triaryl ketones.
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