Medicinal Chemistry of the Noncanonical Cyclic Nucleotides cCMP and cUMP

A method to activate sulfamoyl fluorides, fluorosulfates, and sulfonyl fluorides with calcium triflimide, and DABCO for SuFEx with amines is described. The reaction was applied to a diverse set of sulfamides, sulfamates, and sulfonamides at room temperature under mild conditions. Additionally, we highlight the application of this transformation to parallel medicinal chemistry to generate a broad array of nitrogen-based S(VI) compounds.

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SuFEx Activation with Ca(NTf2)2: A Unified Strategy to Access Sulfamides, Sulfamates and Sulfonamides from S(VI) Fluorides

10.26434/chemrxiv.12026811 ◽

2020 ◽

Author(s):

Subham Mahapatra ◽

Cristian P. Woroch ◽

Todd W. Butler ◽

Sabrina N. Carneiro ◽

Sabrina C. Kwan ◽

...

Keyword(s):

Room Temperature ◽

Medicinal Chemistry ◽

Mild Conditions ◽

Broad Array

A method to activate sulfamoyl fluorides, fluorosulfates, and sulfonyl fluorides with calcium triflimide, and DABCO for SuFEx with amines is described. The reaction was applied to a diverse set of sulfamides, sulfamates, and sulfonamides at room temperature under mild conditions. Additionally, we highlight the application of this transformation to parallel medicinal chemistry to generate a broad array of nitrogen-based S(VI) compounds.

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Cascade CuH-Catalyzed Conversion of Alkynes to Enantioenriched 1,1-Disubstituted Products

10.26434/chemrxiv.7961633.v1 ◽

2019 ◽

Author(s):

De-Wei Gao ◽

Yang Gao ◽

Huiling Shao ◽

Tian-Zhang Qiao ◽

Xin Wang ◽

...

Keyword(s):

Organic Synthesis ◽

Medicinal Chemistry ◽

Proteasome Inhibitors ◽

Building Blocks ◽

Unique Role ◽

Efficient Strategy ◽

Carbon Centers ◽

Rapid Access ◽

Cascade Catalysis ◽

Privileged Scaffolds

Enantioenriched α-aminoboronic acids play a unique role in medicinal chemistry and have emerged as privileged pharmacophores in proteasome inhibitors. Additionally, they represent synthetically useful chiral building blocks in organic synthesis. Recently, CuH-catalyzed asymmetric alkene hydrofunctionalization has become a powerful tool to construct stereogenic carbon centers. In contrast, applying CuH cascade catalysis to achieve reductive 1,1-difunctionalization of alkynes remains an important, but largely unaddressed, synthetic challenge. Herein, we report an efficient strategy to synthesize α-aminoboronates via CuH-catalyzed hydroboration/hydroamination cascade of readily available alkynes. Notably, this transformation selectively delivers the desired 1,1-heterodifunctionalized product in favor of alternative homodifunctionalized, 1,2-heterodifunctionalized, or reductively monofunctionalized byproducts, thereby offering rapid access to these privileged scaffolds with high chemo-, regio- and enantioselectivity.

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