Carbon‐to‐Carbon Anion Relay Chemistry: Facile Generation of Substituted Allyllithium Species

Zheng, Pinguan; Cai, Zhengxin; Garimallaprabhakaran, Aswinkumar; Rooshenas, Parham; Schreiner, Peter R.; Harmata, Michael

doi:10.1002/ejoc.201100783

Cited by 10 publications

(1 citation statement)

References 35 publications

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“…6 However, its potential has not been highlighted for the synthesis of silacycles. As part of our continuing interest in silicon chemistry, 7 we recently became interested in benzosiloline (Scheme 1, top/right), 8 a unique and barely investigated silacycle. This species is structurally related to the well-known benzosiloles (Scheme 1, top/right), 9 which have wide-ranging applications in luminescent materials.…”

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confidence: 99%

Visible light-promoted radical cyclization of silicon-tethered alkyl iodide and phenyl alkyne. An efficient approach to synthesize benzosilolines

Lin

Gan

et al. 2016

Chem. Commun.

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confidence: 99%

Visible light-promoted radical cyclization of silicon-tethered alkyl iodide and phenyl alkyne. An efficient approach to synthesize benzosilolines

Lin

Gan

et al. 2016

Chem. Commun.

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Addition of Non‐Stabilized Carbon‐Based Nucleophilic Reagents to Chiral N ‐Sulfinyl Imines

et al. 2019

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Natural products and pharmaceuticals that contain chiral branched amines are compounds of considerable interest. One strategy for preparing chiral branched amines involves the addition of a nucleophile to an imine bearing a readily cleavable chiral auxiliary. Sulfinamide‐based auxiliaries are well‐suited to this approach because (i) many sulfonamides are commercially available or can be prepared by efficient synthetic methods, (ii) N ‐sulfinyl aldimines and ketimines can be prepared in a straightforward manner, (iii) the chiral amine products are obtained with high diastereomeric ratios across a wide range of carbon‐based nucleophiles, and (iv) the N ‐sulfinyl group is cleaved under mild conditions. This chapter focuses on the addition of non‐stabilized, carbon‐based nucleophiles to N ‐sulfinyl aldimines and ketimines. Specifically, additions of alkyl, alkenyl, aryl, allylic, propargylic, alkynyl, and cyano nucleophiles are presented. Factors that can influence the stereoselectivity of the addition reaction are presented, along with the most prevalent reaction conditions employed for each class of nucleophile. Nucleophilic additions to N ‐sulfinyl aldimines and ketimines are key steps in the syntheses of a number of drug discovery targets and natural products, examples of which are highlighted in this review.

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Bis(difluoromethyl)trimethylsilicate Anion: A Key Intermediate in Nucleophilic Difluoromethylation of Enolizable Ketones with Me₃SiCF₂H

Chen

Zhao

et al. 2016

Angewandte Chemie

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A pentacoordinate bis(difluoromethyl)silicate anion, [Me3Si(CF2H)2]−, is observed for the first time by the activation of Me3SiCF2H with a nucleophilic alkali‐metal salt and 18‐crown‐6. Further study on its reactivity by tuning the countercation effect led to the discovery and development of an efficient, catalytic nucleophilic difluoromethylation of enolizable ketones with Me3SiCF2H by using a combination of CsF and 18‐crown‐6 as the initiation system. Mechanistic investigations demonstrate that [(18‐crown‐6)Cs]+[Me3Si(CF2H)2]− is a key intermediate in this catalytic reaction.

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Carbon‐to‐Carbon Anion Relay Chemistry: Facile Generation of Substituted Allyllithium Species

Cited by 10 publications

References 35 publications

Visible light-promoted radical cyclization of silicon-tethered alkyl iodide and phenyl alkyne. An efficient approach to synthesize benzosilolines

Visible light-promoted radical cyclization of silicon-tethered alkyl iodide and phenyl alkyne. An efficient approach to synthesize benzosilolines

Addition of Non‐Stabilized Carbon‐Based Nucleophilic Reagents to Chiral N ‐Sulfinyl Imines

Bis(difluoromethyl)trimethylsilicate Anion: A Key Intermediate in Nucleophilic Difluoromethylation of Enolizable Ketones with Me₃SiCF₂H

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Carbon‐to‐Carbon Anion Relay Chemistry: Facile Generation of Substituted Allyllithium Species

Cited by 10 publications

References 35 publications

Visible light-promoted radical cyclization of silicon-tethered alkyl iodide and phenyl alkyne. An efficient approach to synthesize benzosilolines

Visible light-promoted radical cyclization of silicon-tethered alkyl iodide and phenyl alkyne. An efficient approach to synthesize benzosilolines

Addition of Non‐Stabilized Carbon‐Based Nucleophilic Reagents to Chiral N ‐Sulfinyl Imines

Bis(difluoromethyl)trimethylsilicate Anion: A Key Intermediate in Nucleophilic Difluoromethylation of Enolizable Ketones with Me3SiCF2H

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Bis(difluoromethyl)trimethylsilicate Anion: A Key Intermediate in Nucleophilic Difluoromethylation of Enolizable Ketones with Me₃SiCF₂H