Palladium‐Catalyzed Desulfitative Sonogashira–Hagihara Cross‐Couplings of Arenesulfonyl Chlorides and Terminal Alkynes

Abstract

Dedicated to Joe Richmond on the occasion of his 60th birthday.Abstract: For the first time, conditions have been found for the palladium-catalyzed desulfitative carbon-carbon cross-coupling of arenesulfonyl chlorides with aryl-and alkylacetylenes. Pd 2 (dba) 3 /P(t-Bu) 3 and CuI provide the best catalyst for reactions in refluxing THF and in the presence of K 2 CO 3 .

Palladium‐Katalysatorsysteme für die Synthese von konjugierten Eninen durch Sonogashira‐Kupplungen und verwandte Alkinylierungen

“…[32] Den Nutzen von Arensulfonylchloriden bei der Sonogashira-Alkinylierung entdeckten Vogel und Dubbaka, die als Katalysatorsystem 3 Mol-% [Pd 2 (dba) 3 ], 10 Mol-% PtBu 3 , 15 Mol-% CuI und 2.5 ¾quivalente K 2 CO 3 in siedendem THF einsetzten; die konkurrierende Alkin-Homokupplung wurde durch die langsame Zugabe eines Alkin-Überschusses zurückge-drängt. [168] In Anbetracht der Leistungsfähigkeit der Heck-Reaktion mit unreaktiven Arylhalogeniden in Gegenwart von Phosphoniumhalogeniden beschrieben Chang und Mitarbeiter den Einsatz von Tetraarylphosphoniumchloriden als Arylierungsreagentien bei Kreuzkupplungen. [169] [169] Den Anwendungsbereich der Sonogashira-Reaktion erweiterte der Einsatz von ungewöhnlichen Halogenidpartnern wie Bromchinoliziniumbromid (Tabelle 26, Nr.…”

Ligandless Iron‐Catalyzed Desulfinylative C–C Allylation Reactions using Grignard Reagents and Alk‐2‐enesulfonyl Chlorides

“…[2] Arene-and alkanesulfonyl chlorides are inexpensive and readily available compounds. We have shown that Stille, carbonylative Stille, [3] SuzukiMiyaura, [4] Sonogashira-Hagihara, [5] Mizoroki-Heck, [6] and Negishi [7] type cross-couplings can be carried out by using sulfonyl chlorides as electrophilic partners under desulfinylative conditions. [8] We have shown also that 2-methylprop-2-ene-(1), prop-2-ene-(2), 1-methylprop-2-ene-(3), and (E)-but-2-enesulfonyl chloride (4) are useful electrophilic partners in desulfinylative palladium-catalyzed C-C coupling reactions with inexpensive Grignard reagents and sodium salts of malonic esters and methyl acetoacetate.…”

The Catalyzed Desulfinylative Allylation of Carbonyl Compounds with Alk‐2‐enesulfonyl Chlorides and Silyl Alk‐2‐enesulfinates

“…[2] Arene-and alkanesulfonyl chlorides are inexpensive and readily available compounds. We have shown that Stille, carbonylative Stille, [3] Suzuki-Miyaura, [4] Sonogashira-Hagihara, [5] MizorokiHeck, [6] and Negishi [7] -type cross-couplings can all be carried out by using sulfonyl chlorides as the electrophilic partners under desulfinylative conditions. [8] We have also shown that 2-methylprop-2-ene-(1), prop-2-ene-(3), and (E)-but-2-enesulfonyl chlorides (4) are useful electrophilic partners in desulfinylative palladium-catalyzed C À C coupling reactions with inexpensive Grignard reagents and sodium salts of malonic esters and methyl acetoacetate.…”