title: Temporal separation of catalytic activities allows anti-Markovnikov reductive functionalization of terminal alkynes.
abstract: There is currently great interest in the development of multistep catalytic processes in which one or several catalysts act sequentially to rapidly build complex molecular structures. Many enzymes--often the inspiration for new synthetic transformations--are capable of processing a single substrate through a chain of discrete, mechanistically distinct catalytic steps. Here, we describe an approach to emulate the efficiency of these natural reaction cascades within a synthetic catalyst by the temporal separation of catalytic activities. In this approach, a single catalyst exhibits multiple catalytic activities sequentially, allowing for the efficient processing of a substrate through a cascade pathway. Application of this design strategy has led to the development of a method to effect the anti-Markovnikov (linear-selective) reductive functionalization of terminal alkynes. The strategy of temporal separation may facilitate the development of other efficient synthetic reaction cascades.
authors.affiliation: Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA.
authors.forename: Le
authors.initials: L
authors.lastname: Li
authors.affiliation: Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA.
authors.forename: Seth B
authors.initials: SB
authors.lastname: Herzon
mesh_terms: D000478:Alkylation; D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D010084:Oxidation-Reduction
chemical_list: D000480:Alkynes