An iterative strategy for the synthesis of oligothiophenes by catalytic cross‐coupling reactions

Abstract

An iterative strategy for the synthesis of new sulfur-functionalized oligothiophenes by Suzuki or Stille cross-coupling reactions was applied to the reaction of 4-bromo-tert-butylphenylthioether with thiophene derivatives. The planarity of the oligothiophenes obtained was confirmed by the singlecrystal X-ray structure analysis of 2-(4 -tert-butylthiophenyl)thiophene, which shows a potentially large electronic conjugation length.

Synthesis of Planar Five‐Connected Nodal Ligands

“…Synthesis of [Fe{(C 5 H 4 P( t Bu) 2 }{C 5 (C 6 H 4 SH) 5 }] (8) : BrC 6 H 4 S t Bu was synthesised as described in literature 46. In a two‐necked flask, a mixture of [Fe(C 5 H 4 {P( t Bu) 2 }(C 5 H 5 )]BF 4 (0.300 g, 0.72 mmol), Pd(OAc) 2 (0.032 g, 0.14 mmol), PPh 3 (0.184 g, 0.72 mmol), BrC 6 H 4 S t Bu (3.172 g, 13.00 mmol) and t BuOK (0.942 g, 8.40 mmol) was placed in toluene (35 mL) and heated under reflux for 2 days.…”

“…Compound 7 (0.048 g, 0.06 mmol) was purified by silica gel chromatography eluting with CH2Cl 2 /EtOH (98:2). ES-HRMS: m/z calcd 867.2532; found: 867.2514 [M + H] + , 1 H NMR (400 MHz, CDCl 3 ): d = 0.99 (d, J = 14.15 Hz, 18 H), 4.70 (m, 2 H), 4.96 (m, 2 H), 7.35 (m, 10 H), 7.65 (m, 10 H), 9.95 ppm (s, 5 H); 31 P{ 1 H} NMR (CD 3 OD): d = 66.7 ppm; IR: ñ = 3363 (m), 2968 (m), 2832 (m), 2736(m), 1694 (l), 1600 (l), 1208 (l), 1167 (m), 1127 (m), 843 (l), 747 (l), 661 (m), 639 (m), 595 cm À1 (m).Synthesis of [FeAC H T U N G T R E N N U N G {(C 5 H 4 PA C H T U N G T R E N N U N G (tBu) 2 }{C 5 A C H T U N G T R E N N U N G (C 6 H 4 SH) 5 }](8): BrC 6 H 4 StBu was synthesised as described in literature [46]. In a two-necked flask, a mixture of[FeA C H T U N G T R E N N U N G (C 5 H 4 {PA C H T U N G T R E N N U N G (tBu) 2 }A C H T U N G T R E N N U N G (C5 H 5 )]BF 4 (0.300 g, 0.72 mmol), PdA C H T U N G T R E N N U N G (OAc) 2 (0.032 g, 0.14 mmol), PPh 3 (0.184 g, 0.72 mmol), BrC 6 H 4 StBu (3.172 g, 13.00 mmol) and tBuOK (0.942 g, 8.40 mmol) was placed in toluene (35 mL) and heated under reflux for 2 days.…”

Synthesis, 1H and 13C NMR assignment and electrochemical properties of novel thiophene–thiazolothiazole oligomers and polymers

“…[14] 3-Hexylthiophene-2-carbaldehyde A solution of 2-bromo-3-hexylthiophene (5.7 g, 0.023 mol) in THF (150 ml) was cooled down to −78…”

Pyridine and Pyrimidine Functionalized Benzene Sulfonic and Disulfonic Acids as New Linker Compounds for Coordination Polymers

“…As the first example, we envisioned to establish the donor functions A and C by Suzuki cross coupling of pyridine boronic acid 1 and bromothiophenol derivative 2 , which was prepared according to a literature procedure (Scheme ) . The tert ‐butyl thioether moiety shall serve as a precursor for a sulfo group.…”

“…[Pd(PPh 3 ) 4 ], 4‐pyridineboronic acid ( 1 ) and 5‐bromopyrimidine ( 10 ) were purchased from TCI. 4‐ tert ‐(Butylthio)bromobenzene ( 2 ), 1‐bromo‐3,5‐bis( tert ‐butylthio)benzene ( 6 ), 4‐ tert ‐(butylthio)benzeneboronic acid ( 11 ), 5‐ethynylpyrimidine ( 21 ) and neopentyl 4‐bromobenzenesulfonate ( 22 ) were synthesized according to literature procedures.…”