98%
921
2 minutes
20
Internal allenes are challenging substrates in copper-catalyzed borylative difunctionalization. When internal allenes featuring a methylidenecyclobutane motif were employed, a copper-catalyzed hydrofunctionalization reaction using diborons and ketones as reaction partners in the presence of a chiral monophosphorus ligand was developed, affording a series of unsaturated chiral tertiary alcohols preserving the methylidenecyclobutane motif in high regio- and stereoselectivities. Control experiments suggest that the reaction involves a boronation-deboronation process, and a plausible mechanism has been proposed.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/acs.orglett.5c01718 | DOI Listing |
Chem Sci
August 2025
Institut für Organische Chemie, Albert-Ludwigs-Universität Freiburg Albertstraße 21 79104 Freiburg im Breisgau Germany
While the vinyl cyclopropane (VCP) scaffold exhibits unique reactivity in chemical transformations, its synthesis presents certain challenges. Herein, we report the visible-light photoredox-catalyzed radical-polar crossover cyclization (RPCC) of terminal and internal allenes with carboxylic acids, realizing the construction of functionalized vinyl cyclopropanes (VCPs) with highly chemo-, and regioselectivities under mild conditions. Moreover, this photoredox protocol exhibits good functional group tolerance, a broad substrate scope, facile scalability and easy rearrangement to give various cyclopentene units.
View Article and Find Full Text PDFOrg Lett
July 2025
Dipartimento di Scienze Chimiche, della Vita e della Sostenibilità Ambientale, Università di Parma, Parco Area delle Scienze 17/A, I-43124 Parma, Italy.
We report an unprecedented iron-catalyzed C-H alkylation of widespread benzamides using readily available allenes. The method, based on cheap, nontoxic, and earth abundant iron catalysts, exploits the assistance of removable triazole directing groups to yield a wide array of internal olefins, even at room temperature, with excellent stereocontrol, good yields, and broad functional group tolerance.
View Article and Find Full Text PDFOrg Lett
June 2025
Department of Chemisty, College of Science, China Agricultural University, 2 Yuanmingyuan West Road, Beijing 100193, People's Republic of China.
Internal allenes are challenging substrates in copper-catalyzed borylative difunctionalization. When internal allenes featuring a methylidenecyclobutane motif were employed, a copper-catalyzed hydrofunctionalization reaction using diborons and ketones as reaction partners in the presence of a chiral monophosphorus ligand was developed, affording a series of unsaturated chiral tertiary alcohols preserving the methylidenecyclobutane motif in high regio- and stereoselectivities. Control experiments suggest that the reaction involves a boronation-deboronation process, and a plausible mechanism has been proposed.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), ISIC-LSCI, Lausanne, Switzerland.
Organic compounds containing a chiral, halogenated aliphatic carbon center are useful in medicinal chemistry, but their enantioselective synthesis remains difficult. Here, we develop a general approach to access these compounds through cobalt-catalyzed hydroalkylation of allenes and alkenes with dihaloamides. The reactions of allenes and terminal alkenes lead to alkylation only at the terminal position.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, Warsaw, 01-224, Poland.
Since its discovery in 1954, the hydrocyanation of multiple carbon-carbon bonds has emerged as a powerful strategy for the synthesis of nitriles. However, the elusive control of selectivity and typical reliance on expensive and toxic transition metal (TM) based catalysts significantly hinder the utility of this process. Here, we report an exclusively regioselective hydrocyanation of unbiased alkynes, driven by base-catalyzed reversible alkyne-allene isomerization and phosphine-catalyzed HCN transfer to the allene.
View Article and Find Full Text PDF