Developing simple and benign protocols for synthesizing alkenylboronates is crucial as they are synthetically valuable compounds in various organic transformations. In this work, we report a straightforward ligand-free protocol for synthesizing alkenylboronates via atom-economical hydroboration of alkynes with HBpin catalyzed by a manganese salt. The reaction shows a high level of chemo and regioselectivity for the terminal alkynes and exclusively produces E-selective alkenylboronates. The hydroboration scope is vast, with the resilience of a range of synthetically beneficial functionalities, such as halides, ether, alkenyl, silyl and thiophenyl groups. This reaction proceeds through the involvement of a metal-hydride intermediate. The developed alkenylboronate can be smoothly converted to useful C-C, C-N and C-I bond-forming reactions.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/asia.202400158 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Recycling e-waste into gold-loaded covalent organic framework catalysts for terminal alkyne carboxylation.
Nat Commun
December 2024
Department of Food Science, College of Agricultural and Life Sciences, Cornell University, Stocking Hall, Ithaca, NY, USA.
The rising demand for gold requires innovative methods for its recovery from e-waste. Here we present the synthesis of two tetrazine-based vinyl-linked covalent organic frameworks: TTF-COF and TPE-COF that adsorb gold ions and nanoparticles and catalyze the carboxylation of terminal alkynes. These covalent organic frameworks have low band gaps and high photocurrent responses.
View Article and Find Full Text PDFTransition-Metal-Free Thioboration of Terminal Alkynes.
JACS Au
December 2024
Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
We present a new type of elementoboration reaction, the thioboration of terminal alkynes. This method enables highly controllable regio-/stereo-/chemoselective - and -thioboration on demand, affording synthetically versatile and densely functionalized vinyl boron/vinyl sulfide derivatives in a straightforward manner without the need for a transition-metal catalyst.
View Article and Find Full Text PDFSelective Synthesis of -Michael Acceptors via Hydroalkylation of Conjugated Alkynes.
J Am Chem Soc
December 2024
Department of Chemistry, University of Washington, Seattle, Washington 98195, United States.
Hydroalkylation of terminal alkynes is a powerful approach to the synthesis of disubstituted alkenes. However, its application is largely unexplored in the synthesis of α,β-unsaturated carbonyls, which are common among synthetic intermediates and biologically active molecules. The thermodynamically less stable -isomers of activated alkenes have been particularly challenging to access because of their propensity for isomerization and the paucity of reliable -selective hydroalkylation methods.
View Article and Find Full Text PDFReversible Bimetallic Inhibition to Modulate Selectivity During Catalysis.
J Am Chem Soc
December 2024
Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Sevilla and Consejo Superior de Investigaciones Científicas (CSIC). Avenida Américo Vespucio 49, 41092 Sevilla, Spain.
Bimetallic complexes have demonstrated a great ability to enhance the activity of monometallic systems for bond activation and catalysis. In this work, we explore the opposite approach: using a second metal to passivate the activity of another by reversible bimetallic inhibition. To do so we have synthesized a family of nine electrophilic gold complexes of formula Au(PR)(NTf) ([NTf] = [N(SOCF)]) that can act as inhibitors in the semihydrogenation of terminal and internal alkynes catalyzed by the iconic iridium Vaska complex IrCl(CO)(PPh).
View Article and Find Full Text PDFVisible-Light-Mediated Radical -Hydroboration of Alkynes with NHC Borane.
J Org Chem
December 2024
School of Pharmaceutical Science, Hengyang Medical School, University of South China, Hengyang 421001, Hunan, China.
Although the radical hydroboration of alkenes with N-heterocyclic carbene (NHC) borane is well documented, the radical hydroboration of alkynes, especially terminal alkynes, remains challenging. Herein, a photoredox-catalyzed radical -hydroboration of alkynes with NHC borane has been developed, which provided various alkenyl boron compounds in moderate to good yields. This protocol exhibits a broad substrate scope, as both internal and terminal alkynes were compatible.
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!