Palladium Catalyzed C–C Coupling Reactions of 3,5-Dichloro-4H-1,2,6-thiadiazin-4-one

Abstract

Palladium catalyzed Suzuki-Miyaura, Stille, and Sonogashira coupling reactions are reported for the electron-deficient heterocyclic scaffold 3,5-dichloro-4H-1,2,6-thiadiazin-4-one (1). Furthermore, 3,5-di(thien-2-yl)-4H-1,2,6-thiadiazin-4-one (7m) is further elaborated to afford the tetrathienyl 3,5-bis[(2,2'-bithien)-5-yl]-4H-1,2,6-thiadiazin-4-one (9). All compounds are fully characterized.

5,5′-Bis[5-(9-decyl-9H-carbazol-3-yl)thien-2-yl]-4H,4′H-[3,3′-bi(1,2,6-thiadiazine)]-4,4′-dione

“…With the Pd coupling chemistry (Stille) of halothiadiazines already investigated [15,19], we selected 5,5′-dichloro-4H,4′H-[3,3′-bi(1,2,6-thiadiazine)]-4,4′-dione (8) as the suitable starting material for preparing a bithiadiazine-containing oligomer. Bithiadiazine 8 can be readily prepared from dichlorothiadiazine 1 in four steps with an overall yield of 47% [20].…”

3,5-Bis(4-dodecylthiophen-2-yl)-4H-1,2,6-thiadiazin-4-one

“…Recently, we described the palladium catalysed Suzuki and Stille coupling reactions of 3,5-dichloro-4H-1,2,6-thiadiazin-4-one 1 which enabled the preparation of symmetrical biaryl and biheteroarylthiadiazinones such as 3,5-di(thiophen-2-yl)-4H-1,2,6-thiadiazin-4-one 3 [7] (Scheme 1). Based on this structural unit we postulated the construction of conjugated polymers such as the OPEN ACCESS M784 (Page 2) thiophene/thiadiazinone polymers.…”

“…Both are useful precursors to several polycyclic 1,2,6-thiadiazine systems [4,5]. For several years now we have been developing the chemistry of both these heterocyclic scaffolds [2][3][4][5][6][7][8][9][10].…”

4H-1,2,6-Thiadiazin-4-one-containing small molecule donors and additive effects on their performance in solution-processed organic solar cells

“…The synthesis of the D-A-D small molecules started from 3,5-dichloro-4H-1,2,6-thiadiazin-4-one (1), that can be readily prepared in two steps from dichloromalononitrile and SCl 2 in multigram quantities, 36 and is a versatile building block that can participate in a range of palladium catalysed C-C coupling reactions such as Stille and Suzuki-Miyaura couplings to give various 3,5-di(het)aryl substituted systems. 37,38 The synthesis and their characterisation appear in the ESI. † All the compounds were readily soluble in tetrahydrofuran (THF) and dichloromethane (DCM).…”