A [(3IP)Pd(allyl)]OTf complex was shown to function efficiently and regioselectively in allene hydrosilylation with phenyl- and diphenylsilane. The catalyst also proved to be highly active for allene hydrosilylation employing a wide range of silanes, each of which produced a single regioisomer.
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http://dx.doi.org/10.1039/c4cc09804h | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077, Hong Kong SAR, China.
Hydroboration of allenes is powerful and atom-economic approach to the synthesis of organoboranes, such as the highly versatile allylboranes. However, regarding regiocontrol, existing methods uniformly deliver the boron functionality to the less hindered β- or γ-position, but not the α-position. The latter is particularly challenging for allenes with substantial steric difference between the two terminals and lacking electronic bias (e.
View Article and Find Full Text PDFJ Org Chem
September 2023
Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, People's Republic of China.
A transition-metal-free hydrosilylation of allenes is reported herein by using commercially available lithium triethylborohydride (LiHBEt) as the catalyst. Both mono- and disubstituted allenes could be hydrosilylated with primary or secondary silanes effectively. This reaction represents an environmental and economic method to prepare ()-allylsilanes in good yields along with decent selectivities.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
March 2023
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, CAS, 345 Lingling Road, Shanghai, 200032, P. R. China.
Here, we report the first example of Ni-catalyzed asymmetric hydrosilylation of 1,1-disubstituted allenes with high level of regioselectivities and enantioselectivities. The key to achieve this stereoselective hydrosilylation reaction was the development of the SPSiOL-derived bisphosphite ligands (SPSiPO). This protocol features broad substrate scope, excellent functional group, and heterocycle tolerance, thus provides a versatile method for the construction of enantioenriched tertiary allylsilanes in a straightforward and atom-economic manner.
View Article and Find Full Text PDFChemistry
December 2022
Department of Chemistry, Center for Sustainable Chemistry, Ghent University, Krijgslaan 281, 9000, Ghent, Belgium.
The synthesis and isolation of [Pd(NHC)(PhC≡CPh)] complexes are reported. These new 14-electron Pd(0)-complexes are key synthons leading to known palladium(0) and palladium(II) species, as well as permitting access to unprecedented mixed NHC-phosphite palladium(0) complexes. This motif permits the facile catalytic hydrosilylation of allenes.
View Article and Find Full Text PDFOrg Lett
August 2022
Department of Chemistry, University of Science and Technology of China, Hefei 230026, P. R. China.
A novel strategy of copper-catalyzed regio- and enantioselective hydrosilylation of 4-substituted vinylidenecyclohexanes with silanes was developed. In this protocol, various allenes and silanes were used to afford the corresponding (cyclohexylidene)ethyl silanes in moderate to high yields with good enantioselectivities.
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