Browse
Submit Data
Databases
API
Help

Dataset Information

29 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Direct stereospecific amination of alkyl and aryl pinacol boronates.

ABSTRACT: The direct amination of alkyl and aryl pinacol boronates is accomplished with lithiated methoxyamine. This reaction directly provides aliphatic and aromatic amines, stereospecifically, and without preactivation of the boronate substrate.

SUBMITTER: Mlynarski SN

PROVIDER: S-EPMC3481838 | biostudies-literature | 2012 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Direct stereospecific amination of alkyl and aryl pinacol boronates.

Mlynarski Scott N SN Karns Alexander S AS Morken James P JP

Journal of the American Chemical Society 20120924 40

The direct amination of alkyl and aryl pinacol boronates is accomplished with lithiated methoxyamine. This reaction directly provides aliphatic and aromatic amines, stereospecifically, and without preactivation of the boronate substrate. ...[more]

PMID: 23002712

Similar Datasets

An Enzymatic Platform for Primary Amination of 1-Aryl-2-alkyl Alkynes.

Project description:Propargyl amines are versatile synthetic intermediates with numerous applications in the pharmaceutical industry. An attractive strategy for efficient preparation of these compounds is nitrene propargylic C(sp3)-H insertion. However, achieving this reaction with good chemo-, regio-, and enantioselective control has proven to be challenging. Here, we report an enzymatic platform for the enantioselective propargylic amination of alkynes using a hydroxylamine derivative as the nitrene precursor. Cytochrome P450 variant PA-G8 catalyzing this transformation was identified after eight rounds of directed evolution. A variety of 1-aryl-2-alkyl alkynes are accepted by PA-G8, including those bearing heteroaromatic rings. This biocatalytic process is efficient and selective (up to 2610 total turnover number (TTN) and 96% ee) and can be performed on preparative scale.

| S-EPMC8765727 | biostudies-literature

A Protocol for Direct Stereospecific Amination of Primary, Secondary, and Tertiary Alkylboronic Esters.

Project description:The direct, stereospecific amination of alkylboronic and borinic esters can be conducted by treatment of the organoboron compound with methoxyamine and potassium tert-butoxide. In addition to being stereospecific, this process also enables the direct amination of tertiary boronic esters in an efficient fashion.

| S-EPMC6322687 | biostudies-literature

Direct Aryl C-H Amination with Primary Amines Using Organic Photoredox Catalysis.

Project description:The direct catalytic C-H amination of arenes is a powerful synthetic strategy with useful applications in pharmaceuticals, agrochemicals, and materials chemistry. Despite the advances in catalytic C-H functionalization, the use of aliphatic amine coupling partners is limited. Described herein is the construction of C-N bonds, using primary amines, by direct C-H functionalization with an acridinium photoredox catalyst under an aerobic atmosphere. A wide variety of primary amines, including amino acids and more complex amines are competent coupling partners. Various electron-rich aromatics and heteroaromatics are useful scaffolds in this reaction, as are complex, biologically active arenes. We also describe the ability to functionalize arenes that are not oxidized by an acridinium catalyst, such as benzene and toluene, thus supporting a reactive amine cation radical intermediate.

| S-EPMC5995118 | biostudies-literature

Suzuki-Miyaura cross-coupling of 3-pyridyl triflates with 1-alkenyl-2-pinacol boronates.

Project description:Palladium-catalyzed Suzuki-type couplings of 3-pyridyl triflates with alkenyl pinacol boronates proceed in good to excellent yield. Optimized conditions use Pd(PPh(3))(4) (10 mol %) as catalyst with K(3)PO(4) (3 equiv) as base in dioxane.

| S-EPMC3080250 | biostudies-literature

Iridium-catalyzed direct asymmetric reductive amination utilizing primary alkyl amines as the N-sources.

Project description:Direct asymmetric reductive amination is one of the most efficient methods for the construction of chiral amines, in which the scope of the applicable amine coupling partners remains a significant challenge. In this study we describe primary alkyl amines effectively serve as the N-sources in direct asymmetric reductive amination catalyzed by the iridium precursor and sterically tunable chiral phosphoramidite ligands. The density functional theory studies of the reaction mechanism imply the alkyl amine substrates serve as a ligand of iridium strengthened by a (N)H-O(P) hydrogen-bonding attraction, and the hydride addition occurs via an outer-sphere transition state, in which the Cl-H H-bonding plays an important role. Through this concise procedure, cinacalcet, tecalcet, fendiline and many other related chiral amines have been synthesized in one single step with high yields and excellent enantioselectivity.

| S-EPMC9187633 | biostudies-literature

Alpha-selective Ni-catalyzed hydroalumination of aryl- and alkyl-substituted terminal alkynes: practical syntheses of internal vinyl aluminums, halides, or boronates.

Project description:A method for Ni-catalyzed hydroalumination of terminal alkynes, leading to the formation of alpha-vinylaluminum isomers efficiently (>98% conv in 2-12 h) and with high selectivity (95% to >98% alpha), is described. Catalytic alpha-selective hydroalumination reactions proceed in the presence of a reagent (diisobutylaluminum hydride; dibal-H) and 3.0 mol % metal complex (Ni(dppp)Cl(2)) that are commercially available and inexpensive. Under the same conditions, but with Ni(PPh(3))(2)Cl(2), hydroalumination becomes highly beta-selective, and, unlike uncatalyzed transformations with dibal-H, generates little or no alkynylaluminum byproducts. All hydrometalation reactions are reliable, operationally simple, and practical and afford an assortment of vinylaluminums that are otherwise not easily accessible. The derived alpha-vinyl halides and boronates can be synthesized through direct treatment with the appropriate electrophiles [e.g., Br(2) and methoxy(pinacolato)boron, respectively]. Ni-catalyzed hydroaluminations can be performed with as little as 0.1 mol % catalyst and on gram scale with equally high efficiency and selectivity.

| S-EPMC2921967 | biostudies-literature

Stereospecific cross-coupling of secondary alkyl ?-trifluoroboratoamides.

Project description:The stereospecific cross-coupling of enantioenriched nonbenzylic secondary alkyl boron compounds has been achieved. The high selectivity toward product formation over an undesired ?-H elimination pathway is achieved via an intramolecular coordination of an ancillary carbonyl to the metal center in the diorganopalladium intermediate.

| S-EPMC3045699 | biostudies-literature

Manganese-Catalyzed Stereospecific Hydroxymethylation of Alkyl Tosylates.

Project description:The development of a stereospecific hydroxymethylation of alkyl tosylates using an inexpensive, first-row catalyst is described. The transformation proceeds under mild conditions with low pressure to deliver homologated alcohols as products. Chiral, nonracemic ?-branched primary alcohols are obtained with high enantiospecificity from easily accessed secondary alkyl substrates. Simple modification of the reaction system also permits access to ?-d2 alcohols. These studies use anionic metal carbonyl catalysis to access a synthetic equivalent of the challenging hydroxymethyl anion from carbon monoxide.

| S-EPMC7147876 | biostudies-literature

Direct, Selective α-Aryloxyalkyl Radical Cyanation and Allylation of Aryl Alkyl Ethers.

Project description:We report the site-selective α-aryloxyalkyl C-H cyanation and allylation of aryl alkyl ethers using an acridinium photocatalyst with phosphate base under LED irradiation (456 nm). Oxidation of the aryl alkyl ether to its corresponding radical cation by the excited stated photocatalyst allowed facile deprotonation of the ArOC(sp3)-H bond to afford an α-aryloxyalkyl radical, which was trapped with sulfone substrates, resulting in expulsion of a sulfonyl radical and formation of allylated or cyanated products.

| S-EPMC10964245 | biostudies-literature

Cu(I)-catalyzed C-H alpha-amination of aryl ketones: direct synthesis of imidazolinones.

Project description:This paper describes an alpha-amination process of aryl ketones using CuCl as catalyst and di-tert-butyldiaziridinone as the nitrogen source. A variety of imidazolinone derivatives are prepared in moderate yields under mild conditions. A possible catalytic cycle is proposed for this reaction.

| S-EPMC2704946 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data