B(C6F5)3‐katalysierte chemoselektive Defunktionalisierung von etherhaltigen primären Alkyltosylaten mit Hydrosilanen

Chatterjee, Indranil; Porwal, Digvijay; Oestreich, Martin

doi:10.1002/ange.201611813

Cited by 18 publications

(2 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…reported a catalytic C( sp 3 )−OTs bond cleavage promoted by a complex of B(C 6 F 5 ) 3 /Et 3 SiH at room temperature. The protocol has excellent chemoselectivity over other functionalities, such as bromide ( 94 ), olefins ( 98 ) (Table ) …”

Section: C‐methylationmentioning

confidence: 99%

Advances in the Synthesis of Methylated Products through Indirect Approaches

Chen

2019

Adv Synth Catal

View full text Add to dashboard Cite

Methylation is a well‐known structural modification in organic and medicinal chemistry. In addition to using conventional methylation reagents for direct methylation, indirect methylation approaches have been also successfully applied, particularly to tackle the isolation difficulty among the methylated product, the unreacted starting material, and the dimethylated by‐product due to the structural similarities between them. This review summarizes recent advances in the synthesis of methylated products through indirect approaches – transforming functionalized intermediates into the methylated products. The indirect methodologies surveyed in this review are useful for chemists to select appropriate methylation strategies, particularly for the challenging synthesis of methylated products at a large scale in drug discovery. Abbreviations: AIBN: azobisisobutyronitrile; Cbz: carbobenzyloxy; DBU: 1,8‐diazabicyclo[5.4.0]undec‐7‐ene; DIBAL: diisobutylaluminium hydride; FA: formic acid; Fmoc: fluorenylmethyloxycarbonyl; KOTMS: potassium trimethylsilanolate; LAH: lithium aluminium hydride; LiHBEt3: lithium triethylborohydride; PC: photocatalyst; PMHS: polymethylhydrosiloxane; PSMS: zinc bis(phenylsulfonylmethanesulfinate); SAM: S‐adenosylmethionine; SET: single electron transfer; TBAF: tetra‐n‐butylammonium fluoride; TBS: tert‐butyldimethylsilyl; TEA: trimethylamine; TFA: trifluoroacetic acid; TMS: trimethylsilyl; Ts: 4‐toluenesulfonyl.

show abstract

Section: C‐methylationmentioning

confidence: 99%

Advances in the Synthesis of Methylated Products through Indirect Approaches

Chen

2019

Adv Synth Catal

View full text Add to dashboard Cite

show abstract

“…[9] Unlike in our previous work, [8] GagnØ suggested as tepwise pathway involving an intramolecular attack of an eighboring alkenyl group at the activated CÀObond of the silaoxonium ion. This pathway takes advantage of anchimeric assistance [10] to generate abenzylic cation with C À Cbond formation. Inspired by these results,w ee nvisioned that homoallylic alcohols bearing an aryl substituent at the C3 position may undergo ac arbocyclization with anchimeric assistance from an adjacent alkenyl group to give cyclobutanes under aB (C 6 F 5 ) 3 / silane catalytic system.…”

mentioning

confidence: 99%

Reductive Carbocyclization of Homoallylic Alcohols to syn‐Cyclobutanes by a Boron‐Catalyzed Dual Ring‐Closing Pathway

et al. 2018

View full text Add to dashboard Cite

The organoborane-catalyzed reductive carbocyclization of homoallylic alcohols has been developed by using hydrosilanes as reducing reagents to provide a range of 1,2-disubstituted arylcyclobutanes. The reaction proceeds in a cis-selective manner with high efficiency under mild conditions. Mechanistic studies, including deuterium scrambling and Hammett studies, and DFT calculations, suggest a dual ring-closing pathway.

show abstract

Catalytic Reductive Pinacol‐Type Rearrangement of Unactivated 1,2‐Diols through a Concerted, Stereoinvertive Mechanism

et al. 2017

View full text Add to dashboard Cite

A catalytic pinacol‐type reductive rearrangement reaction of internal 1,2‐diols is reported herein. Several scaffolds not usually amenable to pinacol‐type reactions, such as aliphatic secondary–secondary diols, undergo the transformation well without the need for prefunctionalization. The reaction uses a simple boron catalyst and two silanes and proceeds through a concerted, stereoinvertive mechanism that enables the preparation of highly enantiomerically enriched products. Computational studies have been used to rationalize the preference for migration over direct deoxygenation.

show abstract

B(C₆F₅)₃‐katalysierte chemoselektive Defunktionalisierung von etherhaltigen primären Alkyltosylaten mit Hydrosilanen

Cited by 18 publications

References 35 publications

Advances in the Synthesis of Methylated Products through Indirect Approaches

Advances in the Synthesis of Methylated Products through Indirect Approaches

Reductive Carbocyclization of Homoallylic Alcohols to syn‐Cyclobutanes by a Boron‐Catalyzed Dual Ring‐Closing Pathway

Catalytic Reductive Pinacol‐Type Rearrangement of Unactivated 1,2‐Diols through a Concerted, Stereoinvertive Mechanism

Contact Info

Product

Resources

About