Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Myoglobin-Catalyzed Olefination of Aldehydes.

ABSTRACT: The olefination of aldehydes constitutes a most valuable and widely adopted strategy for constructing carbon-carbon double bonds in organic chemistry. While various synthetic methods have been made available for this purpose, no biocatalysts are known to mediate this transformation. Reported herein is that engineered myoglobin variants can catalyze the olefination of aldehydes in the presence of ?-diazoesters with high catalytic efficiency (up to 4,900 turnovers) and excellent E?diastereoselectivity (92-99.9?% de). This transformation could be applied to the olefination of a variety of substituted benzaldehydes and heteroaromatic aldehydes, also in combination with different alkyl ?-diazoacetate reagents. This work provides a first example of biocatalytic aldehyde olefination and extends the spectrum of synthetically valuable chemical transformations accessible using metalloprotein-based catalysts.

SUBMITTER: Tyagi V

PROVIDER: S-EPMC4796475 | biostudies-literature | 2016 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Myoglobin-Catalyzed Olefination of Aldehydes.

Tyagi Vikas V Fasan Rudi R

Angewandte Chemie (International ed. in English) 20160114 7

The olefination of aldehydes constitutes a most valuable and widely adopted strategy for constructing carbon-carbon double bonds in organic chemistry. While various synthetic methods have been made available for this purpose, no biocatalysts are known to mediate this transformation. Reported herein is that engineered myoglobin variants can catalyze the olefination of aldehydes in the presence of α-diazoesters with high catalytic efficiency (up to 4,900 turnovers) and excellent E diastereoselecti ...[more]

PMID: 26765247

Similar Datasets

Efficient conversion of primary azides to aldehydes catalyzed by active site variants of myoglobin.

Project description:The oxidation of primary azides to aldehydes constitutes a convenient but underdeveloped transformation for which no efficient methods are available. Here, we demonstrate that engineered variants of the hemoprotein myoglobin can catalyze this transformation with high efficiency (up to 8,500 turnovers) and selectivity across a range of structurally diverse aryl-substituted primary azides. Mutagenesis of the 'distal' histidine residue was particularly effective in enhancing the azide oxidation reactivity of myoglobin, enabling these reactions to proceed in good to excellent yields (37-89%) and to be carried out at a synthetically useful scale. Kinetic isotope effect, isotope labeling, and substrate binding experiments support a mechanism involving heme-catalyzed decomposition of the organic azide followed by alpha hydrogen deprotonation to generate an aldimine which, upon hydrolysis, releases the aldehyde product. This work provides the first example of a biocatalytic azide-to-aldehyde conversion and expands the range of non-native chemical transformations accessible through hemoprotein-mediated catalysis.

| S-EPMC4754990 | biostudies-literature

Reductive olefination of aldehydes via chromium Brook rearrangement.

Project description:[reaction: see text] The combination of CrCl(2) and silyl chlorides converts aryl and conjugated aldehydes into olefinic adducts in good to excellent yields. When constrained by structural features, the intermediate vic-diol can be isolated. Available data are consistent with a novel chromium Brook rearrangement.

| S-EPMC2517130 | biostudies-literature

Silver-Catalyzed Aldehyde Olefination Using Siloxy Alkynes.

Project description:We describe the development of a silver-catalyzed carbonyl olefination employing electron rich siloxy alkynes. This process constitutes an efficient synthesis of trisubstituted unsaturated esters, and represents an alternative to the widely utilized Horner-Wadsworth-Emmons reaction. Excellent diastereoselectivities are observed for a range of aldehydes using either 1-siloxy-1-propyne or 1-siloxy-1-hexyne. This mild catalytic process also enables chemoselective olefination of aldehydes in the presence of either ester or ketone functionality. Furthermore, since no by-products are generated, this catalytic process is perfectly suited for development of sequential reactions that can be carried out in a single flask.

| S-EPMC3837490 | biostudies-literature

Rhodium-Catalyzed Electrooxidative C-H Olefination of Benzamides.

Project description:Metal-catalyzed chelation-assisted C-H olefinations have emerged as powerful tools for the construction of functionalized alkenes. Herein, we describe the rhoda-electrocatalyzed C-H activation/alkenylation of arenes. The olefinations of challenging electron-poor benzamides were thus accomplished in a fully dehydrogenative fashion under electrochemical conditions, avoiding stoichiometric chemical oxidants, and with H2 as the only byproduct. This versatile alkenylation reaction also features broad substrate scope and used electricity as a green oxidant.

| S-EPMC7496262 | biostudies-literature

Rhodium catalyzed template-assisted distal para-C-H olefination.

Project description:Rhodium catalysis has been extensively used for ortho-C-H functionalization reactions, and successfully extended to meta-C-H functionalization. Its application to para-C-H activation remains an unmet challenge. Herein we disclose the first example of such a reaction, with the Rh-catalyzed para-C-H olefination of arenes. The use of a Si-linked cyanobiphenyl unit as a traceless directing group leads to highly para-selective arene-olefin couplings.

| S-EPMC6713868 | biostudies-literature

Pd(II)-catalyzed olefination of sp3 C-H bonds.

Project description:The first Pd(II)-catalyzed sp(3) C-H olefination reaction has been developed using N-arylamide directing groups. Following olefination, the resulting intermediates were found to undergo rapid 1,4-addition to give the corresponding gamma-lactams. Notably, this method was effective with substrates containing alpha-hydrogen atoms and could be applied to effect methylene C-H olefination of cyclopropane substrates.

| S-EPMC2841429 | biostudies-literature

Photoinitiated carbonyl-metathesis: deoxygenative reductive olefination of aromatic aldehydes <i>via</i> photoredox catalysis.

Project description:Carbonyl-carbonyl olefination, known as McMurry reaction, represents a powerful strategy for the construction of olefins. However, catalytic variants that directly couple two carbonyl groups in a single reaction are less explored. Here, we report a photoredox-catalysis that uses B2pin2 as terminal reductant and oxygen trap allowing for deoxygenative olefination of aromatic aldehydes under mild conditions. This strategy provides access to a diverse range of symmetrical and unsymmetrical alkenes with moderate to high yield (up to 83%) and functional-group tolerance. To follow the reaction pathway, a series of experiments were conducted including radical inhibition, deuterium labelling, fluorescence quenching and cyclic voltammetry. Furthermore, NMR studies and DFT calculations were combined to detect and analyze three active intermediates: a cyclic three-membered anionic species, an α-oxyboryl carbanion and a 1,1-benzyldiboronate ester. Based on these results, we propose a mechanism for the C[double bond, length as m-dash]C bond generation involving a sequential radical borylation, "bora-Brook" rearrangement, B2pin2-mediated deoxygenation and a boron-Wittig process.

| S-EPMC6492636 | biostudies-literature

Pd(II)-catalyzed enantioselective C-H olefination of diphenylacetic acids.

Project description:Pd(II)-catalyzed enantioselective C-H olefination of diphenylacetic acid substrates has been achieved through the use of monoprotected chiral amino acid ligands. The absolute configuration of the resulting olefinated products is consistent with that of a proposed C-H insertion intermediate.

| S-EPMC2806936 | biostudies-literature

Olefination of Alkyl Halides with Aldehydes by Merging Visible-Light Photoredox Catalysis and Organophosphorus Chemistry.

Project description:Carbon-carbon double bond (C=C) formation is a crucial transformation in organic chemistry. Visible-light photoredox catalysis provides economical and sustainable opportunities for the development of novel and peculiar organic reactions. Here we report a method for the olefination of alkyl halides with aldehydes by visible-light photoredox catalysis using triphenylphosphine as a reductive quencher (103 examples). This transformation accommodates a variety of aldehydes including paraformaldehyde; aqueous formaldehyde; 2,2,2-trifluoroacetaldehyde monohydrate; 2,2,2-trifluoro-1-methoxyethanol; and other common aldehydes. The present method exhibits several advantages, including operational simplicity, mild reaction conditions, wide functional group tolerance, and amenability to gram-scale synthesis. We anticipate that it will be widely used in the synthesis of organic molecules, natural products, biological molecules, and polymers.

| S-EPMC6137709 | biostudies-literature

Myoglobin-Catalyzed C-H Functionalization of Unprotected Indoles.

Project description:Functionalized indoles are recurrent motifs in bioactive natural products and pharmaceuticals. While transition metal-catalyzed carbene transfer has provided an attractive route to afford C3-functionalized indoles, these protocols are viable only in the presence of N-protected indoles, owing to competition from the more facile N-H insertion reaction. Herein, a biocatalytic strategy for enabling the direct C-H functionalization of unprotected indoles is reported. Engineered variants of myoglobin provide efficient biocatalysts for this reaction, which has no precedents in the biological world, enabling the transformation of a broad range of indoles in the presence of ethyl α-diazoacetate to give the corresponding C3-functionalized derivatives in high conversion yields and excellent chemoselectivity. This strategy could be exploited to develop a concise chemoenzymatic route to afford the nonsteroidal anti-inflammatory drug indomethacin.

| S-EPMC6376986 | 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