Catalytic Oxidative C–H Annulation of Arylthiol Derivatives with 1,3-Diynes toward 3,3′-Bibenzothiophenes

Abstract

Disclosed herein is a catalytic oxidative C−H annulation of thiophenol derivatives with 1,3-diynes, which provides an efficient synthetic approach to both symmetrical and nonsymmetrical 3,3′-bibenzothiophenes. This protocol exhibits a broad substrate scope, excellent functional group tolerance, high regioselectivity, and catalyst-enabled switchable mono/diannulation selectivity. Moreover, three novel helical-type bithiophene heptagonal imides, which are potentially applicable in optoelectronic materials, are constructed based on this reaction.

Regioselective Cobalt(II) Catalyzed C–H Functionalization and [3 + 2] Annulation of N-Arylguanidines with 1,3-Diynes

“…The CH functionalization/1,3-diyne annulation of substrates that contain N and O donors also lead to the formation of interesting spirocyclic compounds, tricyclic N,O heteroaromatics which act as a blue LED . KI catalyzed oxidative CH annulation of thiophenol with 1,3-diynes afforded 3,3′-bibenzothiophenes which act as precursors for helical-type bithiophene heptagonal imides, potential optoelectronic materials …”

Photoinduced Copper(II) Catalyzed Decarboxylative Homocoupling of Arylpropiolic Acids: A Facile Access to the Symmetrical 1,3‐Diynes

“…In other transformations, 2 a was exposed to guanidine hydrochloride, resulting in the production of 4‐benzyl‐6‐phenylpyrimidin‐2‐amine ( 3 c , 51%) [20] . In a similar way, 2 a and diphenyl disulfide combined to generate 2‐phenyl‐3‐(phenylethynyl)benzo[b]thiophene ( 3 d , 79%) [21] . When indole was allowed to react with 2 a , 1‐(1,4‐diphenylbut‐1‐en‐3‐yn‐1‐yl)‐1H‐indole was formed ( 3 e , 93%, mixture of Z ‐ and E ‐isomer in 5 : 2) [22] .…”

“…[20] In a similar way, 2 a and diphenyl disulfide combined to generate 2-phenyl-3-(phenylethynyl)benzo [b]thiophene (3 d, 79%). [21] When indole was allowed to react with 2 a, 1-(1,4diphenylbut-1-en-3-yn-1-yl)-1H-indole was formed (3 e, 93%, mixture of Z-and E-isomer in 5 : 2). [22] Therefore, it is evident that, this 1,3-diynes provides a versatile platform for the synthesis of a broad range of bioactive heterocycle scaffolds.…”

Synthetic progress of organic thermally activated delayed fluorescence emitters via C–H activation and functionalization

“…As an example, DMAC-BBTI (Scheme 60), assembled with donor and acceptor moieties, showed a TADF emission with a small theoretical energy gap (DE ST = 0.026 eV) and good thermal stability, implying the synthetic utility of this oxidative CÀH annulation reaction for fabricating TADF emitters. 283 The innovative CÀH bond transformations discussed in Section 4.6 have disclosed new directions towards simplified yet efficient synthesis of D-A type TADF emitters. The feasible Brønsted acid-catalyzed cyclization between diarylamines and ketones offers advantages such as solvent-free, metal-free, rapid construction, compatibility with various substrates, and suitability for mass production.…”

“…As an example, DMAC-BBTI (Scheme 60), assembled with donor and acceptor moieties, showed a TADF emission with a small theoretical energy gap (Δ E ST = 0.026 eV) and good thermal stability, implying the synthetic utility of this oxidative C−H annulation reaction for fabricating TADF emitters. 283…”