Recent advances and perspectives in ruthenium-catalyzed cyanation reactions

• Thaipparambil Aneeja,
• Cheriya Mukkolakkal Abdulla Afsina,
• Padinjare Veetil Saranya and
• Gopinathan Anilkumar

Beilstein J. Org. Chem. 2022, 18, 37–52, doi:10.3762/bjoc.18.4

• cyanoformate as the cyanide source. They carried out the optimization studies using N,N-dimethylaniline (1.0 mmol) and ethyl cyanoformate (2.0 mmol) as the model substrates and the optimized conditions include 5 wt % Ru/C (20 mg) as catalyst and 2.5 equiv of TBHP (in decane) as oxidant in methanol at 60 °C for

• complexes. From our discussion it is evident that the most commonly used cyanating reagents include highly toxic compounds such as K4[Fe(CN)6], NaCN, CuCN, TMSCN etc. However, some of the reported works involve the use of safer and greener cyanation sources like NCTS, acetone cyanohydrin, ethyl cyanoformate

• methods remains as a limitation in this area. The use of non-toxic and environment friendly cyanating agents such as NCTS, acetone cyanohydrin, ethyl cyanoformate etc needs more attention in future. Scientists can also focus more on cyanation reactions using photoredox catalyst. The larger availability of

Synthesis of eunicellane-type bicycles embedding a 1,3-cyclohexadiene moiety

• Alex Frichert,
• Peter G. Jones and
• Thomas Lindel

Beilstein J. Org. Chem. 2018, 14, 2461–2467, doi:10.3762/bjoc.14.222

•  3). For the synthesis of 25, we started from the known limonene oxide-derived diol 20 [24] that was hydrogenated, oxidized, and silylated at the tertiary alcohol moiety (81%). Reaction of deprotonated 21 with ethyl cyanoformate afforded cyanohydrin 22 by attack of liberated cyanide at the carbonyl

• if there are examples, where this was not the case [21][22]. Access to partially unsaturated eunicellane systems could also be of interest for studies on biosynthesis and chemical interconversion [7][10]. Results and Discussion Dihydrocarvone 9 was converted to the enolate and quenched with ethyl

• cyanoformate in the presence of DMPU affording an inconsequential 5.6:1 mixture of diastereomers favoring 10 (3J3H-4H 12.2 Hz vs 4.8 Hz, Scheme 1). The cyclohexadiene system of 11 was formed after deprotonation of 10 (LiHMDS) and quenching with triflic anhydride. All compounds carrying the 1,3-cyclohexadiene

One-pot synthesis of cyanohydrin derivatives from alkyl bromides via incorporation of two one-carbon components by consecutive radical/ionic reactions

• Shuhei Sumino,
• Akira Fusano,
• Hiroyuki Okai,
• Takahide Fukuyama and
• Ilhyong Ryu

Beilstein J. Org. Chem. 2014, 10, 150–154, doi:10.3762/bjoc.10.12

• bromides and nucleophilic addition of a cyanide ion was investigated, which gave moderate to good yields of cyanohydrin derivatives in one-pot. Keywords: alkyl bromide; carbon monoxide; cyanohydrin; ethyl cyanoformate; multicomponent; radical reaction; Introduction Radical carbonylation reactions have

• ]. The common method to obtain cyanohydrins is the reaction of aldehydes with a cyanide sources such as TMSCN [22][23], ethyl cyanoformate [24][25][26] or acyl cyanide [27][28]. We provide here an efficient one-pot method for the synthesis of cyanohydrin derivatives via consecutive radical/ionic C–C bond

• forming reaction of alkyl bromides, CO and ethyl cyanoformate (Scheme 1, reaction 2). Results and Discussion We examined AIBN-induced radical formylation of 1-bromooctane (1a) with Bu3SnH under 80 atm of CO pressure in the presence of a cyanide source (Scheme 2). Under the employed conditions, the