Cs₂CO₃‐Catalyzed Aerobic Oxidative Cross‐Dehydrogenative Coupling of Thiols with Phosphonates and Arenes

Abstract

An efficient Cs 2 CO 3 -catalyzed oxidative coupling of thiols with phosphonates and arenes that uses molecular oxygen as the oxidant is described. These reactions provide not only an ovel alkali metal salt catalyzeda erobic oxidation, but also an efficient approacht ot hiophosphates and sulfenylarenes,w hich are ubiquitously found in pharmaceuticals and pesticides.T he reaction proceeds under simple and mild reaction conditions,t olerates aw ide range of functional groups,a nd is applicable to the late-stage synthesis and modification of bioactive molecules.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: http://dx.

Synthesis of Thiophosphates by Coupling of Phosphates with Bunte Salts under Mild Conditions

“…thiosulfates were prepared according to the literature procedure. 1 The rest of chemicals were purchased from the Sinopharm Chemical Reagent Co., Adamas, Aladdin and TCI used as received.…”

“…Compound 3aa was obtained in 91.5% yield (47.8mg) according to general procedure 3 as colorless oil. 1 H NMR (400 MHz, CDCl3) δ 7.30 (dq, J = 13.7, 7.2 Hz, 5H), 4.15 -4.05 (m, 2H), 4.04 -3.94 (m, 4H), 1.27 (t, J = 7.1 Hz, 6H). 13 C NMR (101 MHz, CDCl3) δ 137.49, 128.86, 128.62, 127.59, 63.49 (d, J = 5.8 Hz), 34.93 (d, J = 3.9 Hz), 15.93 (d, J = 7.4 Hz).…”

“…O,O-dimethyl S-benzyl thiophosphate (3ab) 2 Compound 3ab was obtained in 90% yield (42.0 mg) according to general procedure 3 as colorless oil. 1 H NMR (400 MHz, CDCl3) δ 7.39 -7.21 (m, 5H), 4.01 (d, J = 14.5 Hz, 2H), 3.68 (d, J = 12.7 Hz, 6H). 13 C NMR (101 MHz, CDCl3) δ 137.34, 128.85, 128.64, 127.66, 53.66 (d, J = 5.6 Hz), 34.87 (d, J = 3.9 Hz).…”

“…31 P NMR (243 MHz, CDCl3) δ 24.14. O,O-diisopropyl S-benzyl thiophosphate (3ac) 1 Compound 3ac was obtained in 80% yield (46.1 mg) according to general procedure 3 as colorless oil. 1 Compound 3ad was obtained in 83% yield (52.5 mg) according to general procedure 3 as colorless oil.…”

“…O,O-diisopropyl S-benzyl thiophosphate (3ac) 1 Compound 3ac was obtained in 80% yield (46.1 mg) according to general procedure 3 as colorless oil. 1 Compound 3ad was obtained in 83% yield (52.5 mg) according to general procedure 3 as colorless oil. 1 H NMR (400 MHz, CDCl3) δ 7.35 -7.28 (m, 4H), 7.25 (dd, J = 5.8, 2.9 Hz, 1H), 4.04 -3.99 (m, 4H), 3.93 (dd, J = 10.0, 7.3 Hz, 2H), 1.62 -1.56 (m, 4H), 1.35 (q, J = 7.5 Hz, 4H), 0.90 (t, J = 7.4 Hz, 6H).…”