Alkylboranes in the Suzuki−Miyaura Coupling:  Stereochemical and Mechanistic Studies

and, Karl Matos; Soderquist, John A.

doi:10.1021/jo971681s

Cited by 333 publications

(235 citation statements)

References 31 publications

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“…Because the C-B bond of A is 'locked' on a specific face of the allyl unit, the reaction is enantiospecific regardless of the three pathways described above. The observed retention of configuration is the outcome of a stereoretentive transmetallation followed by a stereoretentive reductive elimination 44,45 . Whereas the occurrence of enantiomeric erosion is possible in reactions of chiral p-allyl palladium complexes 46,47 , it is observed only to a minimal extent in these sp 3 -sp 2 cross-couplings.…”

Section: Discussionmentioning

confidence: 99%

Synthesis of chiral heterocycles by ligand-controlled regiodivergent and enantiospecific Suzuki Miyaura cross-coupling

2014

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Non-aromatic nitrogen-and oxygen-containing heterocycles such as piperidines and pyrans are prevalent components of natural products and pharmaceutical drugs. Although it has been a workhorse as a synthetic method for assembling unsaturated sp 2 -hybridized substrates, transition metal-catalysed cross-coupling chemistry is traditionally not a suitable approach to prepare chiral non-aromatic heterocycles. Several mechanistic issues hamper the coupling of stereogenic secondary sp 3 -hybridized carbon-metal centres. Moreover, use of unsymmetrical allylic boronates in the Suzuki Miyaura cross-coupling is further complicated by the possibility of forming two regioisomeric products. Here we address this two-pronged problem and demonstrate that chiral enantiomerically enriched heterocyclic allylic boronates can be coupled with high stereochemical retention with a wide variety of aryl and alkenyl halides to independently afford both regioisomeric 2-and 4-substituted dihydropyrans and dehydropiperidines in high selectivity. A divergent mechanism is proposed where regiochemistry is governed by the nature of the ligands on the palladium catalyst. This scalable method is applied to the efficient preparation of the neuroactive alkaloid anabasine and the antidepressant drug paroxetine.

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Section: Discussionmentioning

confidence: 99%

Synthesis of chiral heterocycles by ligand-controlled regiodivergent and enantiospecific Suzuki Miyaura cross-coupling

2014

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“…This study allowed the determination of the stereochemistry of the transmetallation step [170,171] and the role of the base in the catalytic cycle. The main role of base is to generate a more reactive borate 73 by coordination of hydroxide to boron, which will react with the intermediate R-Pd(II)-X complex.…”

Section: Transmetallation In the Suzuki Reactionmentioning

confidence: 99%

“…Soderquist has performed detailed mechanistic studies on the coupling of trialkyl boranes and alkoxy(dialkyl) boranes with aryl and alkenyl electrophiles (Scheme 1-32) [170]. This study allowed the determination of the stereochemistry of the transmetallation step [170,171] and the role of the base in the catalytic cycle.…”

Section: Transmetallation In the Suzuki Reactionmentioning

confidence: 99%

Mechanistic Aspects of Metal‐Catalyzed C—C and C—X Bond‐Forming Reactions

Echavarren

Cárdenas

2005

ChemInform

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Cross-coupling reactions, such as the Stille reaction of organostannanes [1][2][3] and the Suzuki (or Suzuki-Miyaura) cross-coupling of organoboron compounds [4] have settled amongst the more general and selective palladium-catalyzed cross-coupling reactions [5] (Scheme 1-1). These reactions are closely related to other cross-couplings based on transmetallations of a variety of hard or soft organometallic nucleophiles [6] such as the Hiyama [7,8], Sonogashira [9], Kumada (or Kumada-Corriu), and other related couplings [10][11][12].Coupling reactions are somewhat related to the Heck alkenylation of organic electrophiles [13, 14], which is often referred to in the literature as a coupling process. However, although the first steps in both processes are identical, in the Heck reaction there is no transmetallation step. In the alkenylation reaction, the C-C bond is formed by an insertion process, which is followed by a b-hydride elimination to form the substituted alkene product. Cross-coupling (transmetallationbased) processes are a family of closely related catalytic processes that share most mechanistic aspects, although some differences exist on the activation of the organometallic nucleophile. So far, most of the detailed mechanistic studies have cen-

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“…Matos and Soderquist [77] using propargyl bromide for dihydroboration with 9-BBN-H followed by treatment of the adduct with aqueous sodium hydroxide obtained the hydroxy(cyclopropyl)borate complexes, which underwent efficient palladiumcatalyzed cross-coupling to produce a variety of aryl and vinyl cyclopropanes in good to excellent yields via formation of γ-bromoalkylborane 146 [78].…”

Section: Scheme 50mentioning

confidence: 99%

Boranes in Organic Chemistry 3. α-, β- and γ-Haloalkylboranes: The Perspective Vehicles for Organic Synthesis

2016

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<p>The methods of synthesis of α− and β−haloalkylboranes, including chloration of alkylboronic acid esters, additive bromation and chloration of esters of vinyl- and alkenylboronic acids, addition of bromine to trivinylborazines have been considered. The reactions of radical addition of polyhaloidmethanes to vinylboranes, α− and β−unsaturated boronic esters, B-vinyl-B-arylboronic esters, B-trivinyl-B-triarylborazines were discussed. The hydroboration of acetylenic halogenides of dicycloalkylboranes, which led to halocontaining derivatives of dialkylvinylborane was separately considered. The examples of hydroboration of halogenides of allyl and vinyl types are presented. The reaction of dienic synthesis, which takes place between vinylchloroboranes or vinylboronic esters and tetra- or hexachlorocyclopentadienes has been discussed. The reaction of alkenes and allenes with boron tribromide was described. The Markovnikov and non-Markovnikov hydrobromation of boron vinylderivatives has been envisaged. The approaches to the synthesis of perfluoroalkylboranes on the base of hydroboration of perfluoroalkenes have been discussed. The methods of the synthesis of boronates, containing halogetaryl substituents, have been performed. The reactions of hydroboration of halogenides of allylic and propargylic types by 9-borabicyclononane have been shown. The regio- and stereoselectivity of the reaction has been discussed. The examples of the synthesis of boranes of the norbornene type were presented. The reaction of boroallylilation of allyl- and propargylhalogenides leading to the derivatives of 3-bora-bicyclo[3,3,1]-nonane has been discussed. Some directions of using of haloidalkylboranes in the synthesis have been discussed. The examples of nucleophilic substitution leading to oxyalkyl- and azidoalkylboranes have been presented. The route of obtaining of alcohols from α−haloidalkylboranes has been shown. The general scheme of synthesis of α−aminoboronic acids was perfomed. The general approach to the synthesis of allenes on the base of hydroboration products of propargyl halogenides has been discussed. The schemes of synthesis of 1,4-disubstituted-1,2,3-butatrienes are presented. The wide using reaction of introducing of vinylic group into substituent, bonding with boron atom in molecules of dialkylvinylboranes, was discussed. The reactions of new C-C bonds formation, based on the action of iodine on the alkylvinylboronates leading to 1,3-dienes and alkylidencyclanes have been shown. Τhe route of the synthesis of cyclopropanes from β−haloidalkylboranes has been discussed.</p>

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Alkylboranes in the Suzuki−Miyaura Coupling: Stereochemical and Mechanistic Studies

Cited by 333 publications

References 31 publications

Synthesis of chiral heterocycles by ligand-controlled regiodivergent and enantiospecific Suzuki Miyaura cross-coupling

Synthesis of chiral heterocycles by ligand-controlled regiodivergent and enantiospecific Suzuki Miyaura cross-coupling

Mechanistic Aspects of Metal‐Catalyzed C—C and C—X Bond‐Forming Reactions

Boranes in Organic Chemistry 3. α-, β- and γ-Haloalkylboranes: The Perspective Vehicles for Organic Synthesis

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