Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Et₃SiH + KO ^t Bu provide multiple reactive intermediates that compete in the reactions and rearrangements of benzylnitriles and indolenines.

ABSTRACT: The combination of potassium tert-butoxide and triethylsilane is unusual because it generates multiple different types of reactive intermediates simultaneously that provide access to (i) silyl radical reactions, (ii) hydrogen atom transfer reactions to closed shell molecules and to radicals, (iii) electron transfer reductions and (iv) hydride ion chemistry, giving scope for unprecedented outcomes. Until now, reactions with this reagent pair have generally been explained by reference to one of the intermediates, but we now highlight the interplay and competition between them.

SUBMITTER: Smith AJ

PROVIDER: S-EPMC8162870 | biostudies-literature | 2020 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Et3SiH + KO t Bu provide multiple reactive intermediates that compete in the reactions and rearrangements of benzylnitriles and indolenines.

Smith Andrew J AJ Dimitrova Daniela D Arokianathar Jude N JN Clark Kenneth F KF Poole Darren L DL Leach Stuart G SG Murphy John A JA

Chemical science 20201021 45

The combination of potassium tert-butoxide and triethylsilane is unusual because it generates multiple different types of reactive intermediates simultaneously that provide access to (i) silyl radical reactions, (ii) hydrogen atom transfer reactions to closed shell molecules and to radicals, (iii) electron transfer reductions and (iv) hydride ion chemistry, giving scope for unprecedented outcomes. Until now, reactions with this reagent pair have generally been explained by reference to on ...[more]

PMID: 34094446

Similar Datasets

New reductive rearrangement of N-arylindoles triggered by the Grubbs-Stoltz reagent Et3SiH/KO t Bu.

Project description:N-Arylindoles are transformed into dihydroacridines in a new type of rearrangement, through heating with triethylsilane and potassium tert-butoxide. Studies indicate that the pathway involves (i) the formation of indole radical anions followed by fragmentation of the indole C2-N bond, and (ii) a ring-closing reaction that follows a potassium-ion dependent hydrogen atom transfer step. Unexpected behaviors of 'radical-trap' substrates prove very helpful in framing the proposed mechanism.

| S-EPMC8152433 | biostudies-literature

Electron-Transfer and Hydride-Transfer Pathways in the Stoltz-Grubbs Reducing System (KOtBu/Et3 SiH).

Project description:Recent studies by Stoltz, Grubbs et al. have shown that triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reductive cleavage of C-O bonds in aryl ethers and C-S bonds in aryl thioethers. Their extensive mechanistic studies indicate a complex network of reactions with a number of possible intermediates and mechanisms, but their reactions likely feature silyl radicals undergoing addition reactions and SH 2 reactions. This paper focuses on the same system, but through computational and experimental studies, reports complementary facets of its chemistry based on a) single-electron transfer (SET), and b) hydride delivery reactions to arenes.

| S-EPMC5656899 | biostudies-literature

KO t Bu-promoted oxidative dimerizations of 2-methylquinolines to 2-alkenyl bisquinolines with molecular oxygen.

Project description:KO t Bu-promoted oxidative dimerizations of 2-methylquinolines with molecular oxygen as the oxidant have been developed for the first time. The mild reaction conditions allow the homo- and cross-dimerizations of 2-methylquinolines to give functionalized 2-alkenyl bisquinolines in highly trans-selective manners.

| S-EPMC9072141 | biostudies-literature

Facile preparation of organosilanes from benzylboronates and gem-diborylalkanes mediated by KOtBu.

Project description:Methods to efficiently synthesize organosilanes are valuable in the fields of synthetic chemistry and materials science. During the past decades, boron conversion has become a generic and powerful approach for constructing carbon-carbon and other carbon-heteroatom bonds, but its potential application in forming carbon-silicon remains unexplored. Herein, we describe an alkoxide base-promoted deborylative silylation of benzylic organoboronates, geminal bis(boronates) or alkyltriboronates, allowing for straightforward access to synthetically valuable organosilanes. This selective deborylative methodology exhibits operational simplicity, broad substrate scope, excellent functional group compatibility and convenient scalability, providing an effective and complementary platform for the generation of diversified benzyl silanes and silylboronates. Detailed experimental results and calculated studies revealed an unusual mechanistic feature of this C-Si bond formation.

| S-EPMC10321478 | biostudies-literature

Formation and Reactivity of a Hexahydridosilicate [SiH6 ]2- Coordinated by a Macrocycle-Supported Strontium Cation.

Project description:The cationic benzyl complex [(Me4 TACD)Sr(CH2 Ph)][A] (Me4 TACD=1,4,7,10-tetramethyltetraazacyclododecane; A=B(C6 H3 -3,5-Me2 )4 ) reacted with two equivalents of phenylsilane to give the bridging hexahydridosilicate complex [(Me4 TACD)2 Sr2 (thf)4 (μ-κ3 : κ3 -SiH6 )][A]2 (3 a). Rapid phenyl exchange between phenylsilane molecules is assumed to generate monosilane SiH4 that is trapped by two strontium hydride cations [(Me4 TACD)SrH(thf)x ]+ . Complex 3 a decomposed in THF at room temperature to give the terminal silanide complex [(Me4 TACD)Sr(SiH3 )(thf)2 ][A], with release of H2 . Upon reaction with a weak Brønsted acid, CO2 , and 1,3,5,7-cyclooctatetraene SiH4 was released. The reaction of a 1 : 2 mixture of cationic benzyl and neutral dibenzyl complex with phenylsilane gave the trinuclear silanide complex [(Me4 TACD)3 Sr3 (μ2 -H)3 (μ3 -SiH3 )2 ][A], while n OctSiH3 led to the trinuclear (n-octyl)pentahydridosilicate complex [(Me4 TACD)3 Sr3 (μ2 -H)3 (μ3 -SiH5 n Oct)][A].

| S-EPMC9303417 | biostudies-literature

Isolation and Properties of the Long Elusive Deep Blue Soluble [K3 {(Nt Bu)3 S}2 ]. Cage Radical.

Project description:The reaction of potassium metal with sulfurtriimide S(Nt Bu)3 (II) gives the long elusive deep blue cage radical [K3 {(Nt Bu)3 S}2 ]. (1_K) that crystallizes at -35 °C from toluene solution. The subsequent physical characterization via X-ray structure analysis, UV/Vis-, and EPR spectroscopy from solution reveals the existence of one unpaired electron delocalized within the whole cage, i.e. coupling with the six nitrogen atoms, as well as the three potassium atoms caped by the two SN3 ligands. The present X-ray structure analysis further supports previous assumptions made on the parent compound 1_Li obtained from [Li4 {(Nt Bu)3 S}2 ] (I) and finally elucidates the structural arrangement of the SN3 caps and alkali metals in such radical cage species.

| S-EPMC9306764 | biostudies-literature

Au20 (t Bu3 P)8 : A Highly Symmetric Metalloid Gold Cluster in Oxidation State 0.

Project description:Metalloid gold clusters have unique properties with respect to size and structure and are key intermediates in studying transitions between molecular compounds and the bulk phase of the respective metal. In the following, the synthesis of the all-phosphine protected metalloid cluster Au20 (t Bu3 P)8 , solely built from gold atoms in the oxidation state of 0 is reported. Single-crystal X-ray analysis revealed a highly symmetric hollow cube-octahedral arrangement of the gold atoms, resembling gold bulk structure. Quantum-chemical calculations illustrated the cluster can be described as a 20-electron superatom. Optical properties of the compound have shown molecular-like behavior.

| S-EPMC9546110 | biostudies-literature

Isomerization of Functionalized Olefins by Using the Dinuclear Catalyst [PdI (μ-Br)(Pt Bu3 )]2 : A Mechanistic Study.

Project description:In a combined experimental and computational study, the isomerization activity of the dinuclear palladium(I) complex [PdI (μ-Br)(Pt Bu3 )]2 towards allyl arenes, esters, amides, ethers, and alcohols has been investigated. The calculated energy profiles for catalyst activation for two alternative dinuclear and mononuclear catalytic cycles, and for catalyst deactivation are in good agreement with the experimental results. Comparison of experimentally observed E/Z ratios at incomplete conversion with calculated kinetic selectivities revealed that a substantial amount of product must form via the dinuclear pathway, in which the isomerization is promoted cooperatively by two palladium centers. The dissociation barrier towards mononuclear Pd species is relatively high, and once the catalyst enters the energetically more favorable mononuclear pathway, only a low barrier has to be overcome towards irreversible deactivation.

| S-EPMC8596456 | biostudies-literature

Synthesis and Characterization of the Highly Unstable Metalloid Cluster Ag64 (Pn Bu3 )16 Cl6.

Project description:The reduction of (n Bu3 P)AgCl with LiBH(s Bu)3 in toluene gives the metalloid silver cluster Ag64 (Pn Bu3 )16 Cl6 (1) as dark red, temperature- and light-sensitive single crystals in high yield. 1 is the largest structurally characterized metalloid silver cluster exhibiting chlorine and phosphine substituents only. The silver atoms in 1 show an overall brick-shape arrangement, where structural resemblance to the close-packed fcc and hcp structures is realized. Within 1 a 58 electron closed shell system is present. The light sensitivity renders 1 as a model compound for the primary seeds of the photo process, whereby this sensitivity, together with the high-yield synthesis show that 1 is a perfect starting compound for further investigations like silver-plating processes.

| S-EPMC7496867 | biostudies-literature

Radical [1,3] Rearrangements of Breslow Intermediates.

Project description:Breslow intermediates that bear radical-stabilizing N substituents, such as benzyl, cinnamyl, and diarylmethyl, undergo facile homolytic C-N bond scission under mild conditions to give products of formal [1,3] rearrangement rather than benzoin condensation. EPR experiments and computational analysis support a radical-based mechanism. Implications for thiamine-based enzymes are discussed.

| S-EPMC4715472 | biostudies-literature