2.02 Allylsilanes, Allylstannanes, and Related Compounds

Ramachandran, P. V.; Nicponski, Daniel R.; Gagare, Pravin D.

doi:10.1016/b978-0-08-097742-3.00202-0

Cited by 7 publications

(2 citation statements)

References 948 publications

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“…Then N ‐chloroamine and AlFCl 2 are eliminated to give ketone F . AlCl 3 activates F , and 4 a adds to a carbonyl group, affording G [31] . Finally, hydrolysis of G yields product 5 .…”

Section: Figurementioning

confidence: 99%

Sequential C−F Bond Transformation of the Difluoromethylene Unit in Perfluoroalkyl Groups: A Combination of Fine‐Tuned Phenothiazine Photoredox Catalyst and Lewis Acid

Sugihara,

Nishimoto,

Osakada

et al. 2024

Angew Chem Int Ed

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A sequential process via photoredox catalysis and Lewis acid mediation for C–F bond transformation of the CF2 unit in perfluoroalkyl groups has been achieved to transform perfluoroalkylarenes into complex fluoroalkylated compounds. A phenothiazine‐based photocatalyst promotes the defluoroaminoxylation of perfluoroalkylarenes with (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO) under visible light irradiation, affording the corresponding aminoxylated products. These products undergo a further defluorinative transformation with various organosilicon reagents mediated by AlCl3 to provide highly functionalized perfluoroalkyl alcohols. Our novel phenothiazine catalyst works efficiently in the defluoroaminoxylation. Transient absorption spectroscopy revealed that the catalyst regeneration step is crucial for the photocatalytic aminoxylation.

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“…Then N ‐chloroamine and AlFCl 2 are eliminated to give ketone F . AlCl 3 activates F , and 4 a adds to a carbonyl group, affording G [31] . Finally, hydrolysis of G yields product 5 .…”

Section: Figurementioning

confidence: 99%

Sequential C−F Bond Transformation of the Difluoromethylene Unit in Perfluoroalkyl Groups: A Combination of Fine‐Tuned Phenothiazine Photoredox Catalyst and Lewis Acid

Sugihara,

Nishimoto,

Osakada

et al. 2024

Angew Chem Int Ed

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“…An iodine-catalyzed Sakurai reaction, described in the literature as a selective allylation of aldehydes, afforded a complex product mixture as well. Allylation with tributylallylstannane, as well as Brown or Barbier type allylations, also failed. After that the Nozaki–Hiyama–Kishi (NHK) allylation was tried.…”

mentioning

confidence: 99%

A Short Access to the Skeleton of Elisabethin A and Formal Syntheses of Elisapterosin B and Colombiasin A

et al. 2014

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A short stereoselective synthesis of the Elisabethin A skeleton 4 is described, which opens a formal access to the diterpenes Elisapterosin B and Colombiasin A as well. Key reactions were an intermolecular endo-selective Diels-Alder reaction to generate the decalin part of the molecule, a chemo- and diastereoselective allylation of an aldehyde with allylzinc, a palladium ene annulation of the cyclopentane ring, and a novel sulfonium ylide induced fragmentation of a polycyclic ketone. Additional insights have been gained for the crucial epimerization at C-2.

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Recent Advances in the Stereoselective Additions of Allylic Boronates to Carbonyl Compounds

Clement

Hall

2020

Patai's Chemistry of Functional Groups

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The addition of allylboronates to carbonyl compounds remains an invaluable transformation in synthetic organic chemistry for the stereoselective synthesis of a wide variety of substituted homoallylic alcohols. The use of allylboronates is an exceptionally attractive tool, in part due to the stability of organoboron nucleophiles and the inherently high and predictable stereoselectivity consistently observed. Herein, key advances regarding the thermal and catalyzed allylboration of aldehydes and ketones from the past decade are summarized, with a focus on aspects concerning the scope, mechanism, and stereoselectivity. Notably, novel modes of activation are described for both enantioenriched α‐substituted allylboronates and catalytic enantioselective additions of achiral boronates using chiral protic acids and organocatalysts. A number of innovative metal‐catalyzed enantioselective borylation approaches to allylboronates and their subsequent use as substrates, including bimetallic double allylation reagents, are also highlighted. The current innovative progress and limitations in the field of carbonyl allylboration are discussed.

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2.02 Allylsilanes, Allylstannanes, and Related Compounds

Cited by 7 publications

References 948 publications

Sequential C−F Bond Transformation of the Difluoromethylene Unit in Perfluoroalkyl Groups: A Combination of Fine‐Tuned Phenothiazine Photoredox Catalyst and Lewis Acid

Sequential C−F Bond Transformation of the Difluoromethylene Unit in Perfluoroalkyl Groups: A Combination of Fine‐Tuned Phenothiazine Photoredox Catalyst and Lewis Acid

A Short Access to the Skeleton of Elisabethin A and Formal Syntheses of Elisapterosin B and Colombiasin A

Recent Advances in the Stereoselective Additions of Allylic Boronates to Carbonyl Compounds

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