Herein, the copper-catalyzed borylation of readily available acyl chlorides with bis(pinacolato)diboron, (B pin ) or bis(neopentane glycolato)diboron (B neop ) is reported, which provides stable potassium acyltrifluoroborates (KATs) in good yields from the acylboronate esters. A variety of functional groups are tolerated under the mild reaction conditions (room temperature) and substrates containing different carbon-skeletons, such as aryl, heteroaryl and primary, secondary, tertiary alkyl are applicable. Acyl N-methyliminodiacetic acid (MIDA) boronates can also been accessed by modification of the workup procedures. This process is scalable and also amenable to the late-stage conversion of carboxylic acid-containing drugs into their acylboron analogues, which have been challenging to prepare previously. A catalytic mechanism is proposed based on in situ monitoring of the reaction between p-toluoyl chloride and an NHC-copper(I) boryl complex as well as the isolation of an unusual lithium acylBpinOBpin compound as a key intermediate.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC9400893 | PMC |
| http://dx.doi.org/10.1002/chem.202201329 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Merging Copper Catalysis with Nitro Allyl and Allyl Sulfone Derivatives: Practical, Straightforward, and Scalable Synthesis of Diversely Functionalized Allyl Boranes.
JACS Au
January 2025
Laboratoire de Synthèse Organique (LSO-UMR 7652) CNRS, Ecole Polytechnique, ENSTA-Paris, Institut Polytechnique de Paris 828 Bd des Maréchaux, 91128 Palaiseau Cedex, France.
We report here the first example of a copper-catalyzed transformation involving nitro allyl derivatives. This borylation reaction, which exploits the high versatility of the aforementioned precursor, tolerates a variety of functional groups and allows practical, scalable, and highly straightforward access to diversely substituted allylboronic esters in high yields. The method was also extended to allyl sulfones, which provides a very complementary approach, offering additional structural diversity along with improved stereoselectivities.
View Article and Find Full Text PDFEnantioselective Borylcupration/Cyclization of Alkene-Tethered Oxime Esters.
Angew Chem Int Ed Engl
March 2025
Department of Chemistry, University of Toronto, 80 St George St, Toronto, ON M5S 3H6, Canada.
A copper-catalyzed enantioselective synthesis of borylated 1-pyrrolines from γ,δ-unsaturated oxime esters is reported. Twenty-four novel 1-pyrroline derivatives are reported in yields ranging from 26% to 96% and enantioselectivities from 74.5:25.
View Article and Find Full Text PDFEnantioselective 1,4-Borylamination via Copper-Catalyzed Cascade Hydroborylation and Hydroamination of Arylidenecyclopropanes.
J Am Chem Soc
November 2024
State Key Laboratory of Medical Chemical Biology and College of Pharmacy, Nankai University, Tianjin 300071, P. R. China.
Compounds bearing both boryl and amino groups at distal positions are invaluable synthons for synthesizing pharmaceuticals, drug candidates, and natural products, but their catalytic enantioselective synthesis remains rarely explored. We report the first enantioselective 1,4-borylamination reaction through a copper-catalyzed cascade hydroborylation and hydroamination of arylidenecyclopropanes. This reaction combines four readily available components in a highly chemo-, site-, and enantioselective fashion (>20:1 r.
View Article and Find Full Text PDFStereodivergency in Copper-Catalyzed Borylative Difunctionalizations: The Impact of Boron Coordination.
Angew Chem Int Ed Engl
October 2024
Davenport Chemical Laboratories, Department of Chemistry, University of Toronto, 80 St. George St., Toronto, Ontario, M5S 3H6, Canada.
A reagent-controlled diastereodivergent copper-catalyzed borylative difunctionalization is reported. The formation of Lewis adducts that guide selectivity is commonly invoked in organic reaction mechanisms. Using density functional theory calculations, we identified BpinBdan as a sterically similar and less Lewis acidic alternative to Bpin.
View Article and Find Full Text PDFRegioselective C(sp) Carboboration of 1,3-Diynes: A Direct Route to Fully Substituted Enyne Boronates.
Org Lett
August 2024
Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur, West Bengal 721302, India.
Here, we report a general copper-catalyzed C(sp) carboboration of 1,3-diynes, providing access to an array of tetra-substituted boryl enynes in a regioselective manner. All four positions of enyne can be efficiently manipulated using this methodology. The reaction was smoothly applied in the conjugation of complex bioactive molecules to the enyne scaffold.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!