71 research outputs found
A steric tethering approach enables palladium-catalysed C-H activation of primary amino alcohols.
Aliphatic primary amines are a class of chemical feedstock essential to the synthesis of higher-order nitrogen-containing molecules, commonly found in biologically active compounds and pharmaceutical agents. New methods for the construction of complex amines remain a continuous challenge to synthetic chemists. Here, we outline a general palladium-catalysed strategy for the functionalization of aliphatic C-H bonds within amino alcohols, an important class of small molecule. Central to this strategy is the temporary conversion of catalytically incompatible primary amino alcohols into hindered secondary amines that are capable of undergoing a sterically promoted palladium-catalysed C-H activation. Furthermore, a hydrogen bond between amine and catalyst intensifies interactions around the palladium and orients the aliphatic amine substituents in an ideal geometry for C-H activation. This catalytic method directly transforms simple, easily accessible amines into highly substituted, functionally concentrated and structurally diverse products, and can streamline the synthesis of biologically important amine-containing molecules.We are grateful to the Marie Curie Foundation (D.P. & J.C.), EPSRC (T.W.G.), the ERC (V.D.), and the ERC and EPSRC for Fellowships (M.J.G.). We are grateful to Adam Smalley for DFT calculations and Yohei Shimidzu for assistance with optimization of the C–H acetoxylation reaction. Mass spectrometry data was acquired at the EPSRC UK National Mass Spectrometry Facility at Swansea University. The authors declare no competing financial interests.This is the author accepted manuscript. The final version is available from NPG via http://dx.doi.org/10.1038/nchem.236
FIRST EXAMPLES OF THE CONFORMATION CHIRALITY OF HETEROBICYCLO[3.3.0]OCTANES : 3,7-DIOXA-r-1-AZABICYCLO[3.3.0]OCT-c-5-YL-METHOXYPYRAZINES
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ChemInform Abstract: (Masked)serinols: Molecules, Biomolecules, Building Blocks, Supramolecules. Part 1. Syntheses Based on Serinols′ Reactivity with Carbonyl Electrophiles
FIRST SYNTHESIS, ROTAMERISM AND HERBICIDAL EVALUATION OF SUBSTITUTED s-TRIAZINES WITH AMINO-1,3-DIOXANE GROUPS
ChemInform Abstract: Structural and Synthetic Studies in the 4-Phenyl-1,3-dioxane Class. Part 1. Obtaining and Characterization of 5-Chloro-4-phenyl-1,3-dioxanes by Prins Reactions.
ChemInform Abstract: Synthesis and Stereochemistry of Some Heterocyclic Saturated Compounds Based on l-p-Nitrophenylserinol Skeleton. Part 2. 1-Aza-3,7- dioxabicyclo(3.3.0)octanes.
ChemInform Abstract: The Proton Sponge-Triethylamine Tris(hydrogen fluoride) System as a Selective Nucleophilic Fluorinating Reagent for Chlorodiazines.
ChemInform Abstract: Synthesis and Stereochemistry of Some Heterocyclic Saturated Compounds Based on l-p-Nitrophenylserinol Skeleton. Part 1. Ring-Chain Tautomerism of Some Schiff Bases on l-p-Nitrophenylserinol.
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