Organic superbases are a distinct and increasingly utilized class of Brønsted base that possess properties complementary to common inorganic bases. This Concept article discusses recent applications of commercial organic superbases in modern synthetic methodologies. Examples of the advantages of organic superbases in three areas are highlighted, including the discovery of new base‐catalyzed reactions, the optimization of reactions that require stoichiometric Brønsted base, and in high‐throughput experimentation technology.
We
report an operationally simple protocol for the catalytic α-deuteration
of styrenes. This process proceeds via the base-catalyzed reversible
addition of methanol to styrenes in DMSO-d
6 solvent. The concentration of methanol is shown to be critical for
high yields and selectivities over multiple competing side reactions.
The synthetic utility of α-deuterated styrenes for accessing
deuterium-labeled chiral benzylic stereocenters is demonstrated.
We report a general protocol for the direct C−H etherification of N-heteroarenes. Potassium tert-butoxide catalyzes halogen transfer from 2-halothiophenes to N-heteroarenes to form N-heteroaryl halide intermediates that undergo tandem basepromoted alcohol substitution. Thus, the simple inclusion of inexpensive 2-halothiophenes enables regioselective oxidative coupling of alcohols with 1,3-azoles, pyridines, diazines, and polyazines under basic reaction conditions.
The base-catalyzed isomerization of simple aryl halides is presented and utilized to achieve the 4-selective etherification, hydroxylation and amination of 3-bromopyridines. Mechanistic studies support isomerization of 3-bromopyridines to 4-bromopyridines proceeds...
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