A copper-catalyzed regiodivergent hydrosilylation of a wide range of simple allenes is reported. Linear and branched allylsilanes were formed by judicious choice of solvents. Furthermore, branched allylsilanes were obtained with high enantioselectivity (up to 97% enantiomeric excess) with the aid of a C2-symmetric bisphosphine ligand in the unprecedented asymmetric allene hydrosilylation.
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http://dx.doi.org/10.1021/jacs.2c00260 | DOI Listing |
Angew Chem Int Ed Engl
October 2024
Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Department of Chemistry, Northeast Normal University, Changchun, 130024, China.
We herein describe the first example of ligand-controlled, copper-catalyzed regiodivergent asymmetric difunctionalization of terminal alkynes through a cascade hydroboration and hydroallylation process. The catalytic system, consisting of (R)-DTBM-Segphos and CuBr, could efficiently achieve asymmetric 1,1-difunctionalization of aryl terminal alkynes, while ligand switching to (S,S)-Ph-BPE could result in asymmetric 1,2-difunctionalization exclusively. In addition, alkyl substituted terminal alkynes, especially industrially relevant acetylene and propyne, were also valid feedstocks for asymmetric 1,1-difunctionalization.
View Article and Find Full Text PDFOrg Lett
June 2024
Institute of Frontier Chemistry School of Chemistry and Chemical Engineering, Shandong University, Qingdao 266237, P. R. China.
A copper-catalyzed regiodivergent chloropentafluorosulfanylation strategy for 1,3-enynes using SFCl has been developed. The regioselectivity is dictated by the structural and substitution patterns of 1,3-enynes, enabling facile access to three classes of SF-containing products: propargylic chlorides, 1,3-dienes, and allenes. The reaction systems involve radical species, where the transfer of a chlorine atom from SFCl to a carbon radical is considered the predominant pathway.
View Article and Find Full Text PDFNat Commun
October 2023
Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China.
Quaternary amino acids are one of the essential building blocks and precursors of medicinally important compounds. Various synthetic strategies towards their synthesis have been reported. On the other hand, developing core-structure-oriented cross-dehydrogenative coupling (CDC) reactions, is a largely unsolved problem.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2023
State Key Laboratory of Natural Medicines (SKLNM) and Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 210009, P. R. China.
We report herein a regiodivergent and enantioselective allyl addition to ketones with allenylsilanes through copper catalysis. With the combination of CuOAc, a Josiphos-type bidentate phosphine ligand and PhSiH , allyl addition to a variety of ketones furnishes branched products in excellent enantioselectivities. The regioselectivity is completely reversed by employing the P-stereogenic ligand BenzP*, affording the linear products with excellent enantioselectivities and good Z-selectivities.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2023
Department of Biochemistry, The University of Texas Southwestern Medical Center, 5323 Harry Hines Boulevard, Dallas, TX 75390-9038, USA.
We report a copper-catalyzed, regioselective, and stereospecific alkylation of unbiased internal allylic carbonates with functionalized alkyl and aryl Grignard reagents. The reactions exhibit high stereospecificity and regioselectivity for either S 2 or S 2' products under two sets of copper-catalyzed conditions, which enables the preparation of a broad range of products with E-alkene selectivity. Density functional theory calculations reveal the origins of the regioselectivity based on the different behaviors of homo- and heterocuprates.
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