H heterolysis to generate well-defined nickel hydride-proton complexes was achieved by the 2 generation PNP-pincer nickel platform. The regioselective protonation in the ligand framework was demonstrated for the first time to highlight the importance of in-plane hindrance during the H splitting process.
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http://dx.doi.org/10.1039/c9dt03003d | DOI Listing |
J Org Chem
December 2024
College of New Energy, State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580, P. R. China.
The photocatalytic dearomative 1,4-hydroboration of naphthalenes with an N-heterocyclic carbene borane (NHC-BH) complex was reported herein with controllable regioselectivity and chemoselectivity. This protocol yielded a wide range of naphthalene derivatives bearing various functional groups, notably bioactive compounds. Hydroboration occurred through the cooperation of photoredox and hydrogen atom transfer via boryl radical addition to naphthalene and further selective protonation.
View Article and Find Full Text PDFOrg Lett
December 2024
State Key Laboratory of Green Pesticide, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Center for R&D of Fine Chemicals of Guizhou University, Guizhou University, Guiyang 550025, China.
In the chemical synthesis or modification of saccharides, regioselective protection of the many similar OH groups in saccharides is necessary but remains a major challenge. In particular, the regio- and stereoselective conversion of C(1,2)-OH has great synthetic potential in carbohydrate synthesis but has largely remained untapped. Here, an in situ proton-producing system mediated by boronic acid was found and employed for site-selective ketalization of various unprotected saccharides.
View Article and Find Full Text PDFJ Phys Chem A
December 2024
School of Chemical Engineering, University of Science and Technology Liaoning, Qianshan Road 185, Anshan 114051, Liaoning, China.
DFT (M06-2X) calculations were used to study the NHC-catalyzed [3 + 3] cycloaddition of enals with aminoacrylates. The catalytic cycle begins with the binding of the NHC to enal. Subsequent intramolecular proton transfer generates the Breslow intermediate.
View Article and Find Full Text PDFJ Org Chem
November 2024
Key Laboratory of Applied Chemistry of Chongqing Municipality, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, P. R. China.
A novel protocol has been developed for the modular synthesis of polycarbonyl compounds by catalytic hydration of 1,3-diketone-tethered alkynes. The hydration process exhibits good regioselectivity and high yields at room temperature, avoiding the use of strong acids and noble metals and the requirement for elevated temperatures. Mechanistic insights suggest that the hydration proceeds through a concerted process of alkyne protonation and remote carbonyl participation.
View Article and Find Full Text PDFACS Catal
October 2024
Biocatalysis section, Department of Biotechnology, Delft University of Technology, van der Maasweg 9, Delft 2629 HZ, the Netherlands.
Ene reductases (EREDs) catalyze asymmetric reduction with exquisite chemo-, stereo-, and regioselectivity. Recent discoveries led to unlocking other types of reactivities toward oxime reduction and reductive C-C bond formation. Exploring nontypical reactions can further expand the biocatalytic knowledgebase, and evidence alludes to yet another variant reaction where flavin mononucleotide (FMN)-bound ERs from the old yellow enzyme family (OYE) have unconventional activity with α,β-dicarbonyl substrates.
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