Lithium-promoted hydroboration of alkynes and alkenes using commercially available hexamethyldisilazane lithium as a precatalyst and HBpin as a hydride source has been developed. This method will be appealing for organic synthesis because of its remarkable substrate tolerance and good yields. Mechanistic studies revealed that the hydroboration proceeds through the in situ-formed BH species, which acts to drive the turnover of the hydroboration of alkynes and alkenes.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.joc.1c03012 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
-Ge/B 1,1-Hydroboration of Alkynylgermanes with 9-BBN.
Org Lett
January 2025
Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China.
A 1,1-hydroboration of alkynylgermanes with unique -Ge/B stereochemistry under transition-metal-free conditions is reported. Mechanistic studies suggest that a pathway involving α-boration followed by a stepwise 1,2-Ge/H shift on the intermediate structurally lies between an alkyne-Ge π complex and a typical vinyl cation. The resulting Ge/B bimetallic modules, along with a /Ge/B trimetallic variant, can be conveniently transformed into trisubstituted olefins through iterative divergent cross-coupling.
View Article and Find Full Text PDFZero-Valent Copper Catalysis Enables Regio- and Stereoselective Difunctionalization of Alkynes.
Angew Chem Int Ed Engl
January 2025
Jain University - Ramanagara Campus, Centre for Nano and Material Sciences, Jakkasandra Post Kanakapura Taluk, Ramanagara-562112, Bangalore, 562112, Bangalore, INDIA.
The development of a metallic copper-based catalyst system remains a significant challenge. Herein, we report the synthesis of highly stable, active, and reusable Cu0 catalyst for the carboboration of alkynes using carbon electrophiles and bis(pinacolato)diboron (B2pin2) as chemical feedstocks to afford di- and trisubstituted vinylboronate esters in a regio- and stereoselective manner with appreciable turnover number (TON) of up to 2535 under mild reaction conditions. This three-component coupling reaction works well with a variety of substituted electrophiles and alkynes with broad functional group tolerance.
View Article and Find Full Text PDFAsymmetric gem-Hydroboration and gem-Hydrogenation of Ynamides: A New Gateway to Chiral Fischer Carbene Complexes and their Catalytic Transformations.
Angew Chem Int Ed Engl
January 2025
Max-Planck-Institut für Kohlenforschung, 45470, Mülheim/Ruhr, Germany.
Ynamides, when reacted with H or HBpin in the presence of [Cp*RuCl], convert into chiral-at-metal Fischer carbenes by regioselective gem-hydrogenation or gem-hydroboration of the polarized triple bond, respectively. gem-Hydroboration concomitantly affords a carbogenic borylated stereocenter adjacent to the ruthenium carbene unit, the configuration of which can be controlled using an Evans auxiliary. These are the first examples of asymmetric gem-addition reactions to alkynes known in the literature; representative pianostool ruthenium carbene complexes formed by this unconventional route were characterized by crystallographic and spectroscopic means.
View Article and Find Full Text PDFVisible-Light-Mediated Radical -Hydroboration of Alkynes with NHC Borane.
J Org Chem
January 2025
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 PDFSynthesis of Os Hydride Complexes Supported by the Diarylamido/Bis(phosphine) PNP Ligand and Attempts at Using (PNP)Ru and (PNP)Os Complexes in C-H Borylation Catalysis.
Organometallics
November 2024
Department of Chemistry, Texas A&M University, College Station, Texas 77842, United States.
This manuscript describes the synthesis of Os complexes supported by the diarylamido/bis(phosphine) PNP pincer ligand. Compound (PNP)OsH(CO) () was prepared by analogy with the previously reported . However, attempts to make (PNP)OsH () analogously to resulted in the formation of an unexpected compound () that is a product of addition of a BH unit across the Os-N bond in .
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!