The palladium-catalyzed desulfitative cyanation of arenesulfonyl chlorides and sodium sulfinates

Abstract

A palladium-catalyzed desulfitative cyanation of arenesulfonyl chlorides and sodium sulfinates has been developed, providing aryl nitriles in moderate to excellent yields. It represents a facile procedure to access aryl nitriles.

Cobalt‐Catalyzed Electrophilic Cyanation of Arylzinc Halides with N‐Cyano‐N‐phenyl‐p‐methylbenzenesulfonamide (NCTS)

“…Va riousc yanide sources,s uch as CuCN, [5] KCN, [6] NaCN, [7] Zn(CN) 2 , [8] TMSCN, [9] acetone cyanohydrin [10] or K 4 [Fe(CN) 6 ] [11] have been reacted with functionalized aryl halides to provide the corresponding aryl nitriles.H owever, some limitations remain:t he high affinity of the cyanide ion towards the catalyst implies high catalyst loading, the toxicity of the cya-nide reagents,a nd the generation of HCN.T hen, alternativeroutes for the cyanation reactions employing "non-CN-unit" were described but they also generally require as toichiometrica mount of metal salt and harsh conditions. Va riousc yanide sources,s uch as CuCN, [5] KCN, [6] NaCN, [7] Zn(CN) 2 , [8] TMSCN, [9] acetone cyanohydrin [10] or K 4 [Fe(CN) 6 ] [11] have been reacted with functionalized aryl halides to provide the corresponding aryl nitriles.H owever, some limitations remain:t he high affinity of the cyanide ion towards the catalyst implies high catalyst loading, the toxicity of the cya-nide reagents,a nd the generation of HCN.T hen, alternativeroutes for the cyanation reactions employing "non-CN-unit" were described but they also generally require as toichiometrica mount of metal salt and harsh conditions.…”

Highly active recyclable heterogeneous nanonickel ferrite catalyst for cyanation of aryl and heteroaryl halides

“…All of the compounds were characterized by comparing their melting points and FT‐IR, 1 H NMR and 13 C NMR spectra with those found in the literature or by comparing them with the data obtained from available pure compounds purchased from Merck and Aldrich …”

Palladium and TEMPO as Co‐Catalysts in a Desulfinative Homocoupling Reaction

“…Subsequently, sulfinates have received increased attention after early reports on their coupling reactions by Garves,26 and Selke and Thiele27 that used stoichiometric amounts of palladium were largely overlooked. The use of sulfinates in Heck‐like transformations,28–32 addition reactions to (hetero)double bonds and triple bonds,33–39 direct arylations40–42 and related reactions,43 have in common the replacement of the electrophilic cross‐coupling partner with an aryl sulfinate. The ability to replace the nucleophilic coupling partner with sulfinates is an emerging field of research only preceded by a patent from the 1990s;44–49 many of these contributions were reported by the group of Deng.…”