Facile Preparation of α-Aryl Nitriles by Direct Cyanation of Alcohols with TMSCN Under the Catalysis of InX<sub>3</sub>

Chen, Gang; Wang, Zheng; Wu, Jiang; Ding, Kuiling

doi:10.1021/ol801812a

Cited by 86 publications

(38 citation statements)

References 60 publications

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“…[58] Finally, the catalytic addition of TMSCN (Scheme 1, n) to a variety of benzylic alcohols promoted by InBr 3 was reported recently by Ding. [59] Using 5-10 mol-% of InBr 3 as the catalyst, a variety of benzylic alcohols could be converted into the corresponding nitriles in 5-30 min with yields of 46-99 %. An interesting direct formation of the C-C bond between propargylic alcohol 6 and allyl indium reagents has been reported.…”

Section: Indiummentioning

confidence: 99%

Direct Nucleophilic S_N1‐Type Reactions of Alcohols

et al. 2010

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In 2005, the ACS Green Chemistry Institute (GCI) and the global pharmaceutical corporations developed the ACS GCI Pharmaceutical Roundtable to encourage the development of green chemistry and green engineering in the pharmaceutical industry. The Roundtable has established a list of key research areas including the direct nucleophilic reactions of alcohols. The substitution of activated alcohols is a frequently used approach for the preparation of active pharmaceutical ingredients. Alcohols are transformed into the reactive halides or sulfonate esters, thereby allowing their reaction with nucleophiles. Although the direct nucleophilic substitution of an alcohol should be an attractive process, as one of the byproducts from the reaction yields water, hydroxide is a poor leaving group that hinders the reaction. Recently, the direct substitution of allylic, benzylic, and tertiary alcohols has been achieved through an SN1 reaction with catalytic amounts of Brønsted or Lewis acids. In this review, the approaches leading to a greener process are examined in detail, and the advances achieved to date in this important transformation are presented.

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Section: Indiummentioning

confidence: 99%

Direct Nucleophilic S_N1‐Type Reactions of Alcohols

et al. 2010

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“…Starting point for the synthesis was the generation of a tertiary alcohol 6 by the two‐fold Grignard addition to ethyl formate. The alcohol was consecutively transformed to the corresponding nitrile 7 by treatment with trimethylsilyl cyanide via indium(III) bromide catalysis . Propargylation was followed by a Sonogashira coupling with the additional aryl moiety.…”

Section: Resultsmentioning

confidence: 99%

Different Selectivities in the Insertions into C(sp²)−H Bonds: Benzofulvenes by Dual Gold Catalysis Competition Experiments

Plajer

Ahrens

Wieteck

et al. 2018

Chemistry A European J

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An unprecedented, often almost quantitative access to tricyclic aromatic compounds by dual gold catalysis was developed. This synthetic route expands the scope of benzofulvene derivatives through a C(sp )-H bond insertion in easily available starting materials. The insertion takes place with an exclusive chemoselectivity with respect to the competing aromatic C-H positions. A bidirectional synthesis with two competing ortho-aryl C-H bonds in the selectivity-determining step also shows perfect selectivity; this result is explained by a computational investigation of the two conceivable intermediates. The intramolecular competition of two non-equivalent aryl C-H bonds with a benzylic methyl group also showed perfect selectivity.

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“…Having successfully completed the total synthesis of dictyodendrin E ( 5 ) from intermediate 6b , we then conducted the transformation of compound 6b into 6a (Scheme ). Reduction of intermediate 6b with LiAlH 4 followed by treatment of the resulting alcohol with TMSCN (TMS = trimethylsilyl) in the presence of InCl 3 provided the desired cyanide (i.e., 42 ) 26. However, the conversion of cyanide 42 into ester 6a failed.…”

Section: Resultsmentioning

confidence: 99%

Total Synthesis of Dictyodendrins B and E, and Formal Synthesis of Dictyodendrin C

2014

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A full account of the concise total syntheses of dictyodendrins B and E, and the formal synthesis of dictyodendrin C are described. A palladium‐catalysed Larock indole synthesis was used to form the highly substituted indole core, and a palladium‐mediated one‐pot consecutive Buchwald–Hartwig amination/C–H activation reaction was used to construct the key pyrrolo[2,3‐c]carbazole core. Unsuccessful synthetic strategies are also discussed.

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Facile Preparation of α-Aryl Nitriles by Direct Cyanation of Alcohols with TMSCN Under the Catalysis of InX₃

Cited by 86 publications

References 60 publications

Direct Nucleophilic S_N1‐Type Reactions of Alcohols

Direct Nucleophilic S_N1‐Type Reactions of Alcohols

Different Selectivities in the Insertions into C(sp²)−H Bonds: Benzofulvenes by Dual Gold Catalysis Competition Experiments

Total Synthesis of Dictyodendrins B and E, and Formal Synthesis of Dictyodendrin C

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Facile Preparation of α-Aryl Nitriles by Direct Cyanation of Alcohols with TMSCN Under the Catalysis of InX3

Cited by 86 publications

References 60 publications

Direct Nucleophilic SN1‐Type Reactions of Alcohols

Direct Nucleophilic SN1‐Type Reactions of Alcohols

Different Selectivities in the Insertions into C(sp2)−H Bonds: Benzofulvenes by Dual Gold Catalysis Competition Experiments

Total Synthesis of Dictyodendrins B and E, and Formal Synthesis of Dictyodendrin C

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Facile Preparation of α-Aryl Nitriles by Direct Cyanation of Alcohols with TMSCN Under the Catalysis of InX₃

Direct Nucleophilic S_N1‐Type Reactions of Alcohols

Direct Nucleophilic S_N1‐Type Reactions of Alcohols

Different Selectivities in the Insertions into C(sp²)−H Bonds: Benzofulvenes by Dual Gold Catalysis Competition Experiments