Reactions of 3-(p-substituted-phenyl)-5-chloromethyl-1,2,4-oxadiazoles with KCN leading to acetonitriles and alkanes via a non-reductive decyanation pathway

• Akın Sağırlı and
• Yaşar Dürüst

Beilstein J. Org. Chem. 2018, 14, 3011–3017, doi:10.3762/bjoc.14.280

• trisubstituted 1,2,4-oxadiazol-5-ylacetonitriles and their parent alkanes, namely, 1,2,3-trisubstituted-1,2,4-oxadiazol-5-ylpropanes. To the best of our knowledge, the current synthetic route leading to decyanated products will be the first in terms of a decyanation process which allows the transformation of

• compounds were identified by means of IR, 1H NMR, 13C NMR, 2D NMR spectra, TOF–MS and X-ray measurements. Keywords: decyanation; KCN; 1,2,4-oxadiazole; Introduction Heterocyclic scaffolds bearing 1,2,4-oxadiazole rings have been the subject of an increasing and remarkable attention due to their various

• exploited by providing very limited structural data [19]. Interestingly, increasing the reaction temperature to 100 °C yielded 1,2,4-oxadiazole-substituted propanes 4 as the major products which can only be interpreted via a decyanation pathway of cyanated oxadiazoles 3 (Figure 2). Up to date, various

The reductive decyanation reaction: an overview and recent developments

• Jean-Marc R. Mattalia

Beilstein J. Org. Chem. 2017, 13, 267–284, doi:10.3762/bjoc.13.30

• Jean-Marc R. Mattalia Aix-Marseille Univ, CNRS, Centrale Marseille, iSm2, Marseille, France 10.3762/bjoc.13.30 Abstract This review presents an overview of the reductive decyanation reaction with a special interest for recent developments. This transformation allows synthetic chemists to take

• advantages of the nitrile functional group before its removal. Mechanistic details and applications to organic synthesis are provided. Keywords: α-aminonitrile; decyanation; electron donor; hydride; malononitrile; transition metal catalysis; Introduction Many strategies in organic synthesis involve the

• removal of the cyano group from cyclic substrates [8], in 2006 we published a review reporting various methods allowing the reductive decyanation reaction that transforms organic nitriles into the parent alkane [9]. Even if chemical procedures previously described are still of relevance in organic

One-pot synthesis of 4′-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling

• Roman Yu. Peshkov,
• Elena V. Panteleeva,
• Wang Chunyan,
• Evgeny V. Tretyakov and
• Vitalij D. Shteingarts

Beilstein J. Org. Chem. 2016, 12, 1577–1584, doi:10.3762/bjoc.12.153

• of the cyanophenyl fragment of dianion 12− into the para-position of nitrile 2a with the formation of cyclohexadienyl anion 3 after rapid decyanation of the primary cross-coupling dianionic product. Next, the alkylation of intermediate 3 occurs at the position ipso to the cyano group. This

• irreversible decyanation of dianion 10 with the formation of long-living monoanion 3i, and the alkylation of anion 3i at the position ipso to the cyano group providing alkyldihydro product 11, which undergoes fast dehydrocyanation in basic reaction media thus forming final aromatic product 5ia. The high ipso

The Shono-type electroorganic oxidation of unfunctionalised amides. Carbon–carbon bond formation via electrogenerated N-acyliminium ions

• Alan M. Jones and
• Craig E. Banks

Beilstein J. Org. Chem. 2014, 10, 3056–3072, doi:10.3762/bjoc.10.323

• Scheme 14 [78]. (+)-Myrtine (66) is a member of the trans-4,9a-quinolizidin-2-one family, originally isolated from Vaccinium myrtillis (Ericaceae). The synthesis relied on the introduction of a cyano group followed by α-deprotonation by LDA and installation of a methyl group. Reductive decyanation of the

A reductive coupling strategy towards ripostatin A

• Kristin D. Schleicher and
• Timothy F. Jamison

Beilstein J. Org. Chem. 2013, 9, 1533–1550, doi:10.3762/bjoc.9.175

• demonstrated to be a competent substrate for the nickel(0)-catalyzed coupling with a model epoxide. Several synthetic approaches toward the C10−C26 epoxide have been pursued. The C13 stereocenter can be set by allylation and reductive decyanation of a cyanohydrin acetonide. A mild, fluoride-promoted

• decyanation step. We planned to synthesize 5 by reaction of the cyanohydrin acetonide 67 with the epoxide electrophile 66 (Figure 8) [67]. The dimethyl derivative of L-malic acid was chemoselectively reduced with borane-dimethylsulfide and sodium borohydride to afford diol 69 (Scheme 18) [68]. The primary

• coupling, oxy-Michael addition to an enone, and iodocyclization methods. Fluoride-promoted decarboxylation of TMSE esters was identified as a mild strategy enabling simple aldol reactions for the construction of the C15−C16 bond. Allylation and reductive decyanation of a lithiated cyanohydrin acetonide was