Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Diversity-oriented synthesis leads to an effective class of bifunctional linchpins uniting anion relay chemistry (ARC) with benzyne reactivity.

ABSTRACT: In conjunction with the construction of a diversity-oriented synthesis library of 10-membered ring "natural product-like" macrolides, the design, synthesis, and validation of a unique class of bifunctional linchpins, uniting benzyne reactivity initiated by type II anion relay chemistry (ARC) has been achieved, permitting access to diverse [2+2], [3+2], and [4+2] cycloadducts.

SUBMITTER: Smith AB

PROVIDER: S-EPMC3084103 | biostudies-literature | 2011 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Diversity-oriented synthesis leads to an effective class of bifunctional linchpins uniting anion relay chemistry (ARC) with benzyne reactivity.

Smith Amos B AB Kim Won-Suk WS

Proceedings of the National Academy of Sciences of the United States of America 20110118 17

In conjunction with the construction of a diversity-oriented synthesis library of 10-membered ring "natural product-like" macrolides, the design, synthesis, and validation of a unique class of bifunctional linchpins, uniting benzyne reactivity initiated by type II anion relay chemistry (ARC) has been achieved, permitting access to diverse [2+2], [3+2], and [4+2] cycloadducts. ...[more]

PMID: 21245309

Similar Datasets

Benzyl and phenylthiomethyl silanes: a new class of bifunctional linchpins for type II anion relay chemistry (ARC).

Project description:A new class of bifunctional linchpins bearing electrophilic sites beta or gamma to a silyl group have been designed, synthesized, and demonstrated to be competent in tricomponent unions exploiting Type II Anion Relay Chemistry (ARC). High diastereoselectivities were observed when a phenyl moiety (R(2)) served as an anion-stabilizing group (ASG) adjacent to a methyl susbtituent (R(1)), while diastereomeric mixtures were obtained when a phenylthiol moiety served as the ASG, irrespective of alpha-substitution.

| S-EPMC2844645 | biostudies-literature

Uniting anion relay chemistry with Pd-mediated cross coupling: design, synthesis and evaluation of bifunctional aryl and vinyl silane linchpins.

Project description:Union of type II Anion Relay Chemistry (ARC) with Pd-induced Cross Coupling Reactions (CCR) has been achieved, in conjunction with the design, synthesis, and evaluation of a new class of bifunctional linchpins, comprising a series of vinyl silanes bearing beta- or gamma-electrophilic sites. The synthetic tactic permits both alkylation and Pd-mediated CCR of the anions derived via 1,4-silyl C(sp(2))-->O Brook Rearrangements.

| S-EPMC2813984 | biostudies-literature

Through-bond/through-space anion relay chemistry exploiting vinylepoxides as bifunctional linchpins.

Project description:The development of new bifunctional linchpins that permit the union of diverse building blocks is essential for the synthetic utility of anion relay chemistry (ARC). The design, synthesis, and validation of three vinylepoxide linchpins for through-bond/through-space ARC are now reported. For negative charge migration, this class of bifunctional linchpins employs initial through-bond ARC by an SN 2' reaction, followed by through-space ARC exploiting a 1,4-Brook rearrangement. The trans-disubstituted vinylepoxide linchpin yields a mixture of E/Z isomers, whereas the cis-disubstituted and the trans-trisubstituted vinylepoxide linchpins proceed to deliver three-component adducts with excellent E selectivity.

| S-EPMC3969824 | biostudies-literature

Long-range anion relay chemistry (LR-ARC): a validated ARC tactic.

Project description:The design, synthesis, and validation of linchpins for Anion Relay Chemistry (ARC) capable of iterative silyl group migrations have been achieved. This tactic permits "long-range" relocation of negative charge across space, to generate reactive distal nucleophilic centers for both alkylation and palladium-catalyzed coupling reactions.

| S-EPMC3528832 | biostudies-literature

Type?II Anion Relay Chemistry: Exploiting Bifunctional Weinreb Amide Linchpins for the One-Pot Synthesis of Differentiated 1,3-Diketones, Pyrans, and Spiroketals.

Project description:The design, synthesis, and validation of new highly effective bifunctional linchpins for type?II anion relay chemistry (ARC) has been achieved. The mechanistically novel negative-charge migration that comprises the Brook rearrangement is now initiated by a stabilized tetrahedral intermediate, which is generated by nucleophilic addition to a Weinreb amide, rather than by a simple oxyanion that is generated from an epoxide. As a result, the linchpin preserves the carbonyl functionality in the ARC adducts, thus permitting access to functionally complex systems in a single flask without the need for further chemical manipulations. This tactic was validated with the one-pot preparation of monoprotected 1,3-diketones as well as pyran and spiroketal scaffolds, depending on the choice of nucleophile, electrophile, and work-up conditions.

| S-EPMC4726982 | biostudies-literature

?-Silyl Amides: Effective Bifunctional Lynchpins for Type I Anion Relay Chemistry.

Project description:Lynchpins comprising ?-silyl amides have been validated for type I anion relay chemistry (ARC) to permit ready access to ?-ketoamides. Importantly, the ARC protocol can be run at ambient temperature without the need of additional reagents to trigger the [1,4] Brook rearrangement.

| S-EPMC5712993 | biostudies-literature

Diversity-oriented synthesis of 2,4,6-trisubstituted piperidines via type II anion relay chemistry.

Project description:An effective, general protocol for the Diversity-Oriented Synthesis (DOS) of 2,4,6-trisubstituted piperidine congeners has been designed and validated. The successful strategy entails a modular approach to all possible stereoisomers of the selected piperidine scaffold, exploiting Type II Anion Relay Chemistry (ARC), followed in turn by intramolecular S(N)2 cyclization, chemoselective removal of the dithiane moieties and carbonyl reductions.

| S-EPMC3135908 | biostudies-other

Validation of diethoxyphosphonate as an effective agent for charge transfer in Anion Relay Chemistry (ARC).

Project description:The diethoxyphosphonate group comprises an effective agent to achieve negative charge migration in Type II Anion Relay Chemistry (ARC). The process involves a [1,4]-phosphorus-Brook rearrangement that proceeds via a phosphacyclic intermediate leading to an anion that can be captured by reactive electrophiles. In the absence of an exogenous electrophile, the anion derived via phosphorus migration undergoes internal displacement of the phosphonate group to produce a diastereomeric mixture of cyclopropanes.

| S-EPMC3439805 | biostudies-literature

Total Synthesis of (-)-Mandelalide A Exploiting Anion Relay Chemistry (ARC): Identification of a Type II ARC/CuCN Cross-Coupling Protocol.

Project description:Anion relay chemistry (ARC), an effective, multicomponent union tactic, was successfully employed for the total synthesis of the highly cytotoxic marine macrolide (-)-mandelalide A (1). The northern hemisphere was constructed via a new type II ARC/CuCN cross-coupling tactic, while the southern hemisphere was secured via a highly efficient four-component type I ARC union. Importantly, the synthesis of 1 showcases ARC as a rapid, scalable coupling strategy for the union of simple readily available building blocks to access diverse complex molecular fragments with excellent stereochemical control.

| S-EPMC4819492 | biostudies-literature

A unified synthetic strategy to the Cryptocarya family of natural products exploiting Anion Relay Chemistry (ARC).

Project description:A unified synthetic strategy to the Cryptocarya family of natural products has been achieved employing four-component fragment unions in a "single flask" exploiting Anion Relay Chemistry (ARC). Functionalization of the ARC adducts permits rapid construction of five polyhydroxylated di- and tetrahydropyrone natural products of the Cryptocarya class (1-5), in a total of 7-9 steps from commercially available materials.

| S-EPMC3671372 | 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