Metal‐Free Preparation of α‐H‐Chlorinated Alkylaromatic Hydrocarbons by Sunlight

Gaspa, Silvia; Valentoni, Antonio; Mulas, G.; Porcheddu, Andrea; Luca, Lidia De

doi:10.1002/slct.201801168

Cited by 20 publications

(4 citation statements)

References 43 publications

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“…Among other potential complications, the susceptibility of the toluene solvent to radical chlorination at the methyl CÀ H bond was suspected to be a source of side-reactions. [18] Considering these results, we searched for conditions and a suitable solvent to expedite the slow aldehyde to acyl azide transformation (steps B/C, Scheme 1). Indeed, a screen of alternative solvents revealed chlorobenzene as a particularly efficient and relatively green option for this one-pot reaction sequence (see SI, Figure S3).…”

Section: Resultsmentioning

confidence: 99%

One‐Pot Conversion of Benzyl Alcohols to N‐Protected Anilines and Alkyl Alcohols to Carbamoyl Azides

Kobayashi,

Yamaguchi,

Yamamoto

et al. 2023

Eur J Org Chem

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One‐pot, scalable procedures converting benzylic or aliphatic alcohols to various N‐functionalized amines are reported in 38‐83% overall yields. These multi‐step conversions are relatively economic and involve the oxidative formation of acid chloride intermediates and the Curtius rearrangement of acyl azides. Notable aspects of economy include: (1) the use of a relatively green solvent (chlorobenzene) that tolerates both ionic and radical reactions, without the need for rigorously dry or O2‐free conditions; (2) the use of minimal amounts of trichloroisocyanuric acid (TCCA) as a cheap and green chlorinating agent to oxidize the alcohol starting materials and then transform the aldehyde intermediates to acid chlorides under photoirradiation for azide addition; (3) the efficient capture of isocyanate intermediates by alcohol or azide nucleophiles providing N‐protected anilines or N‐protected alkylamines, respectively, the latter of which was employed in the synthesis of an anti‐dementia drug, memantine hydrochloride, over two purification steps.

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Section: Resultsmentioning

confidence: 99%

One‐Pot Conversion of Benzyl Alcohols to N‐Protected Anilines and Alkyl Alcohols to Carbamoyl Azides

Kobayashi,

Yamaguchi,

Yamamoto

et al. 2023

Eur J Org Chem

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“…Further, Luca et al [ 45 ] in 2018 introduced photocatalytic α‐H chlorination of alkyl aromatic and alkyl heteroaromatic hydrocarbons (Scheme 17). The reported process is therefore constituted as metal and additive‐free, with very high yields.…”

Section: Oxidative Transformations (C–cl and C–o)mentioning

confidence: 99%

A new outlook in oxidative transformations and coupling reactions via in situ generation of organic chloramines

Govada

Reddy

2022

Applied Organom Chemis

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Owing to their various modes of coordinating and oxidizing reactivity, organic chloramines represent versatile building blocks for the synthesis of an ample range of multiatomic organic compounds. The present review focuses on synthetic methodologies using their dichotomous nature, which is the basis of their reactivity as oxidant and substrate. This is the first ever review covering the extensive applications of this large class of N–Cl compounds (organic chloramines) especially using one‐pot reaction strategies for various organic transformations, and construction of bonds such as chlorination (C–Cl, S–Cl), oxidation (C=O), cross‐coupling (C–N, CONR, S–N), cyclization, substitution, rearrangement, and catalysis, have been described, briefly to highlight important aspects of the organic chloramines in organic synthesis.

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“…The starting materials were purchased from Sigma-Aldrich and used without further purification, except for compounds 1b , 1c - d 3 , 1d , 1e , 1f , 1h , 1j , 6a , and 6b which were prepared as described in the literature. Reactions were followed by analytical thin-layer chromatography (TLC) Merck DC Kieselgel performed using silica gel 60 (230–400 mesh) aluminum sheets, and visualization was achieved by UV (254 nm) or using stain vanillin solution.…”

Section: Experimental Sectionmentioning

confidence: 99%

Green Approach for Visible-Light-Induced Direct Functionalization of 2-Methylquinolines

et al. 2020

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A transition metal-and oxidant-free visible light-photoinduced protocol for direct functionalization of 2methylquinolines has been developed. This protocol enabled the C−H functionalization of substituted 2-methylquinolines with diacetyl or ethyl pyruvate, under environmentally friendly conditions. A mechanistic investigation based on density functional theory (DFT) calculations provided details about the origins of reactivity and selectivity.

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Metal‐Free Preparation of α‐H‐Chlorinated Alkylaromatic Hydrocarbons by Sunlight

Abstract: A metal and additive free process for the synthesis of benzyl chloride and a-chloro alkyl arenes is reported. The proposed methodology can be carried out by the use of sunlight. The yield and conversion of the obtained benzyl chlorides are very high.

Cited by 20 publications

References 43 publications

One‐Pot Conversion of Benzyl Alcohols to N‐Protected Anilines and Alkyl Alcohols to Carbamoyl Azides

One‐Pot Conversion of Benzyl Alcohols to N‐Protected Anilines and Alkyl Alcohols to Carbamoyl Azides

A new outlook in oxidative transformations and coupling reactions via in situ generation of organic chloramines

Green Approach for Visible-Light-Induced Direct Functionalization of 2-Methylquinolines

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