Study of the Rh₂(OAc)₄‐ or BF₃·OEt₂‐Mediated Reaction of Thioacetic S‐Acid with α‐Diazocarbonyl Compounds

Abstract

The Rh2(OAc)4‐catalyzed reaction of methyl aryldiazoacetates with thioacetic S‐acid gives exclusively the S−H insertion products in high yields, while the corresponding reaction mediated by BF3·OEt2 gives O‐esters. The mechanism of the reaction is discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003

Urea‐Induced Acid Amplification: A New Approach for Metal‐Free Insertion Chemistry

“…Even alkyl thiols were accommodated under the reaction conditions affording SH insertion products 6 f and g in good yield. Thioacids, which are problematic in SH insertions catalyzed by BF 3 ⋅ OEt 2 ,13 were tolerated, providing only the S ‐bound insertion adducts 6 h and i .…”

Iron-Catalyzed Synthesis of Sulfur-Containing Heterocycles

“…The organic layers were combined, dried over MgSO 4 , and filtered, and the solvents were removed under reduced pressure to give an orange oil, which was purified by flash column chromatography (pentane/EtOAc = 3:2) to yield thioether 8b (119 mg, 71%) as a colorless oil as a 1:1 mixture of diastereomers: R f = 0.33 (PE/EtOAc = 3:2); IR (neat) 3347,1600,1491,1452,1415,1193,1054,1011,967, 910 cm −1 ; 1 H NMR (CDCl 3 , 400 MHz) δ 7.39−7.20 (m, 10H), 5.74− 5.62 (m, 2H), 5.15 (br d app , J = 4.0 Hz, 1H), 3.88 (m, 1H), 3.80 (br q app , J = 5. 6 Hz,2H),3.11 (m,1H), 2.99 (m, 1H), 2.72 (br d, J = 3.0 Hz, 0.5H), 2.52 (br d, J = 3.1 Hz, 0.5H), 2.42 (br t, J = 6.2 Hz, 0.5H), 2.33 (br t, J = 6.4 Hz, 0.5H); 13 [127.9 and 127.8], [127.733 and 127.725], [127.3 and 127.2], [126.3 (2C) and 126.2 (2C)], [74.51 and 74.50], [65.80 and 65.78], [51.59 and 51.58], [32.9 and 32.8] 13),252 (12),146 (53),145 (13),131 (15),130 ([PhC 4 H 5 ] •+ , 98), 129 (32), 128 (10), 123 (100), 121 (22), 117 (11), 105 (49), 104 (18), 103 (27), 91 (34), 79 (11) (E)-2-((4-Hydroxy-4-phenylbut-2-en-1-yl)thio)phenol (8c). To a stirred solution of 2-mercaptophenol (55 μL, 0.53 mmol, 1.1 equiv) in EtOH (2.5 mL) was added a solution of NaOH (39 mg, 0.97 mmol, 2.0 equiv) in H 2 O (0.5 mL), and the resulting mixture was stirred at rt for 10 min.…”

rac-2,2′-(Thiane-2,6-diyl)bis[1-(4-bromophenyl)ethanone]

“…For the synthesis of 1,9-bis(4-bromophenyl)nona-2,7-diene-1,9-dione, see: Yang, Cauble et al (2004); Yang, Felton et al (2004). For the synthesis of compounds containing sulfur, see: Knapp et al (2002); Yao et al (2003); Oliveira et al (1999). For applications of natural products containing sulfur, see: Qi et al (2004); Zhang & Zhang (2006); Barco et al (2006).…”

“…The mothods for the synthesis of compounds containing sulfur have been described (Knapp et al, 2002;Yao et al, 2003;Oliveira et al 1999). Natural products containing sulfur often have biological activity, so that the methods for their synthesis have received considerable attention among researchers.…”