Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Type II Anion Relay Chemistry: Conformational Constraints To Achieve Effective [1,5]-Vinyl Brook Rearrangements.

ABSTRACT: The design, synthesis, and evaluation of bifunctional linchpins, conformationally anchored on six-membered rings to achieve efficient [1,5]-Brook rearrangements involving vinyl silanes have been achieved. The restrained linchpins were subsequently exploited in type II anion relay chemistry (ARC) to permit both alkylations and Pd-mediated cross-coupling reactions (CCR) of sp2 stabilized carbanions. DFT calculations were then employed to understand the mechanism and reactivity trends of [1,4]- and [1,5]-vinyl Brook rearrangements to provide insight on the role of the required copper reagent and the substrate geometry.

SUBMITTER: Liu Q

PROVIDER: S-EPMC5558205 | biostudies-literature | 2017 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Type II Anion Relay Chemistry: Conformational Constraints To Achieve Effective [1,5]-Vinyl Brook Rearrangements.

Liu Qi Q Chen Yu Y Zhang Xiao X Houk K N KN Liang Yong Y Smith Amos B AB

Journal of the American Chemical Society 20170614 25

The design, synthesis, and evaluation of bifunctional linchpins, conformationally anchored on six-membered rings to achieve efficient [1,5]-Brook rearrangements involving vinyl silanes have been achieved. The restrained linchpins were subsequently exploited in type II anion relay chemistry (ARC) to permit both alkylations and Pd-mediated cross-coupling reactions (CCR) of sp<sup>2</sup> stabilized carbanions. DFT calculations were then employed to understand the mechanism and reactivity trends of ...[more]

PMID: 28613847

Similar Datasets

Anion Relay Chemistry: Development of an Effective Diastereoselective [3+2] Annulation Tactic Exploiting an Aldol/Brook Rearrangement/Cyclization Cascade.

Project description:An effective [3+2] annulation tactic for the construction of diverse bicyclic compounds possessing highly functionalized cyclopentane rings has been developed employing soft ketone enolates as the initial nucleophile for anion relay chemistry (ARC). The protocol entails a highly diastereoselective aldol/Brook rearrangement/cyclization cascade.

| S-EPMC5836311 | 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

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

?-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

Total Synthesis of (-)-Secu'amamine A Exploiting Type II Anion Relay Chemistry.

Project description:A total synthesis of (-)-secu'amamine A has been achieved exploiting Type II Anion Relay Chemistry (ARC) to provide the full linear carbon and nitrogen skeleton in a single flask with the requisite stereochemistry and functionality. A mechanistic rationale is also proposed to account for the stereochemical outcome of the key aldol reaction leading to the advanced aza tricyclic core.

| S-EPMC4633699 | 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

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

Merging Asymmetric [1,2]-Additions of Lithium Acetylides to Carbonyls with Type II Anion Relay Chemistry.

Project description:An enantioselective three-component coupling reaction has been developed, enabling the union of a variety of lithium acetylides and electrophiles exploiting an achiral linchpin via an anionic reaction cascade. This Type II Anion Relay Chemistry tactic is initiated via an enantioselective [1,2]-carbonyl addition exploiting BINOL catalysis to access an enantioenriched alkoxide intermediate. Migration of charge across the linchpin via a [1,4]-Brook rearrangement with electrophile capture affords a three-component propargyl ether adduct. Herein, we report the development, scope, and limitations of this reaction sequence.

| S-EPMC7307215 | biostudies-literature

Synthetic Access to the Mandelalide Family of Macrolides: Development of an Anion Relay Chemistry Strategy.

Project description:The mandelalides comprise a family of structurally complex marine macrolides that display significant cytotoxicity against several human cancer cell lines. Presented here is a full account on the development of an Anion Relay Chemistry (ARC) strategy for the total synthesis of (-)-mandelalides A and L, the two most potent members of the mandelalide family. The design and implementation of a three-component type II ARC/cross-coupling protocol and a four-component type I ARC union permits rapid access respectively to the key tetrahydrofuran and tetrahydropyran structural motifs of these natural products. Other highlights of the synthesis include an osmium-catalyzed oxidative cyclization of an allylic 1,3-diol, a mild Yamaguchi esterification to unite the northern and southern hemispheres, and a late-stage Heck macrocyclization. Synthetic mandelalides A and L displayed potent cytotoxicity against human HeLa cervical cancer cells (EC50, 1.3 and 3.1 nM, respectively). This synthetic approach also provides access to several highly potent non-natural mandelalide analogs, including a biotin-tagged mandelalide probe for future biological investigation.

| S-EPMC5910188 | biostudies-literature

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

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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