Tungsten-Catalyzed Allylation of Sulfonyl Hydrazides: Regioselective Synthesis of Branched Allylic Sulfones

Abstract

A highly regioselective tungsten (W)-catalyzed allylic sulfonylation of allylic carbonates with readily available sulfonyl hydrazides has been developed. Under tungsten catalysis, a variety of allylic sulfones can be delivered with the help of 4,4′-di-tert-butyl-2,2′-bipyridine in moderate to good yields with excellent b/l regioselectivities. This approach features mild conditions, broad substrate scope, where aryl- and alkyl-substituted allylic carbonates and sulfonyl hydrazides are suitable substrates. This noble-metal-free catalyst system exhibits high reactivity and regioselectivity for the construction of C–S bond.

Keywords

Allylic substitution - Noble-metal-free catalysis - Tungsten - C–S formation - Sulfone

• References

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• 21 Typical Procedure: A pressure tube equipped with a magnetic stir bar was charged with W(CO)₆ (10 mol%), L2 (10 mol%). The tube was purged with argon for 3 minutes. DCE (2 mL) was added followed by the corresponding allylic carbonate (0.6 mmol, 1.5 equiv) and sulfonyl hydrazides (0.4 mmol, 1.0 equiv). The tube was sealed with a PTFE lined cap and was stirred in an oil bath at 60 °C for 24 h. After cooled down, the crude reaction mixture was directly subjected to flash column chromatography (silica gel, PE/EtOAc = 10:1) to afford the allylic sulfone 3a. Colorless solid, 79.6 mg, 85%. TLC R_f = 0.2 (PE:EA 10:1). ¹H NMR (600 MHz, CDCl₃) δ 7.71 (d, J = 7.6 Hz, 2H), 7.32 (d, J = 7.5 Hz, 2H), 5.60 (m, 1H), 5.28 (d, J = 10.1 Hz, 1H), 5.05 (d, J = 17.1 Hz, 1H), 3.48 (t, J = 9.6 Hz, 1H), 2.44 (s, 3H), 2.04 (s, 1H), 1.72–1.57 (m, 1H), 1.43 (s, 1H), 1.25 (t, J = 17.8 Hz, 1H), 0.90 (t, J = 7.1 Hz, 3H). ¹³C NMR (151 MHz, CDCl₃) δ 144.5, 134.6, 130.5, 129.4, 129.2, 123.3, 69.8, 28.9, 21.6, 19.8, 13.5. HRMS (ESI) calcd for C₁₃H₁₈O₂SH ([M+H]): 239.1100. Found: 239.1108.