We report a mild, fast, and convenient catalytic system for the coupling of aryl chlorides with primary, secondary, as well as previously challenging tertiary alkyl thiols using an air-stable nickel(II) precatayst in combination with the low-cost base potassium acetate at room temperature. This catalytic system tolerates a variety of functional groups and enables the generation of thioethers for a wide range of substrates, including pharmaceutical compounds in excellent yields. Chemoselective functionalization of disubstituted substrates was demonstrated. Kinetic and NMR studies, as well as DFT computations support a Ni(0)/Ni(II) catalytic cycle and identify the oxidative addition product as the resting state. Acetate coordination and subsequent acetate facilitated formation of a thiolate complex via internal deprotonation play a key role in the catalytic cycle.
This review summarizes the more recent methods for the synthesis of thioethers using homogeneous metals as catalysts. The thioether moiety can be found in numerous compounds for pharmaceutical, agricultural or material applications and it is therefore important to develop new, efficient methods for their synthesis. The recent efforts in this field focus on the use of non-precious metal catalysts, as well as on the development of new bond-forming processes.
1 Introduction
2 Cross-couplings
3 C-H Activation
4 Hydrothiolation
5 Carbothiolation
6 Miscelaneous
7 Conclusion
We report a nickel catalyzed C−S cross-coupling of aryl and alkenyl triflates with alkyl thiols. A variety of the corresponding thioethers were synthesized using an air-stable nickel precatalyst under mild reaction conditions with short reaction times. A broad substrate scope, including pharmaceutically relevant compounds, could be demonstrated.
We report a nickel catalyzed C-S cross-coupling of aryl and alkenyl triflates with alkyl thiols. A variety of the corresponding thioethers were synthesized using an air-stable nickel precatalyst under mild reaction conditions with short reaction times. A broad substrate scope, including pharmaceutically relevant compounds, could be demonstrated.
We report a mild, fast and convenient catalytic system for the coupling of aryl chlorides with primary, secondary, as well as previously challenging tertiary alkyl thiols using an air-stable nickel(II) precatayst in combination with the low-cost base potassium acetate at room temperature. This new catalytic system tolerates a variety of functional groups and enables the generation of thioethers for a wide range of substrates, including pharmaceutical compounds in excellent yields. Chemoselec-tive functionalization of disubstituted substrates was demonstrated. Kinetic and NMR-studies, as well as DFT computations support a Ni(0)/Ni(II) catalytic cycle and identify the oxidative addition product as the resting state. Acetate coordination and subsequent acetate facilitated formation of a thiolate complex via internal deprotonation play a key role in the catalytic cycle.
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