Cobalt Precursors for High-Throughput Discovery of Base Metal Asymmetric Alkene Hydrogenation Catalysts

Friedfeld, Max R.; Shevlin, Michael; Hoyt, Jordan M.; Krska, Shane W.; Tudge, Matthew T.; Chirik, Paul J.

doi:10.1126/science.1243550

Cited by 359 publications

(189 citation statements)

References 42 publications

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“…In the former area, exciting developments include recent advances in organocatalysis [1] and base metal catalysis. [2] In the latter, the number and scope of enzymatic transformations continues to expand, particularly with advances in the directed evolution of protein catalysts in “the third wave of biocatalysis.” [3] …”

Section: Introductionmentioning

confidence: 99%

Exploiting Enzymatic Dynamic Reductive Kinetic Resolution (DYRKR) in Stereocontrolled Synthesis

Applegate

Berkowitz

2015

Adv Synth Catal

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Over the past two decades, the domains of both frontline synthetic organic chemistry and process chemistry and have seen an increase in crosstalk between asymmetric organic/organometallic approaches and enzymatic approaches to stereocontrolled synthesis. This review highlights the particularly auspicious role for dehydrogenase enzymes in this endeavor, with a focus on dynamic reductive kinetic resolutions (DYRKR) to “deracemize” building blocks, often setting two stereocenters in so doing. The scope and limitations of such dehydrogenase-mediated processes are overviewed, as are future possibilities for the evolution of enzymatic DYRKR.

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Section: Introductionmentioning

confidence: 99%

Exploiting Enzymatic Dynamic Reductive Kinetic Resolution (DYRKR) in Stereocontrolled Synthesis

Applegate

Berkowitz

2015

Adv Synth Catal

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“…The principal targets in these efforts have been the first-row transition metals. Indeed, the groups of Chirik (5,6), Morris (7), Beller (8), and others (9) have developed remarkably active and selective catalysts based on Fe.…”

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confidence: 99%

Metal-free transfer hydrogenation of olefins via dehydrocoupling catalysis

Pérez

Caputo

Dobrovetsky

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

145

111

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A major advance in main-group chemistry in recent years has been the emergence of the reactivity of main-group species that mimics that of transition metal complexes. In this report, the Lewis acidic phosphonium salt [(C 6 F 5 ) 3 PF][B(C 6 F 5 ) 4 ] 1 is shown to catalyze the dehydrocoupling of silanes with amines, thiols, phenols, and carboxylic acids to form the Si-E bond (E = N, S, O) with the liberation of H 2 (21 examples). This catalysis, when performed in the presence of a series of olefins, yields the concurrent formation of the products of dehydrocoupling and transfer hydrogenation of the olefin (30 examples). This reactivity provides a strategy for metalfree catalysis of olefin hydrogenations. The mechanisms for both catalytic reactions are proposed and supported by experiment and density functional theory calculations. fluorophosphonium A wide range of commodity chemicals, petrochemicals, pharmaceuticals, materials, and foods depend on industrial-scale hydrogenation reactions. Catalysts for this process are based on both heterogeneous transition metals materials and homogeneous transition metal complexes. Indeed, it was the discovery of Sabatier (1) in the early 20th century that revealed the utility of amorphous Ni and other metals in hydrogenation processes. Following the dawn of organometallic chemistry in the 1960s, homogeneous catalysts were developed principally based on precious metals (2-4). Although subsequent modifications and optimizations have led to numerous highly selective and efficient catalyst technologies, concerns over cost, natural abundance, and toxicity have prompted efforts to uncover catalysts based on "earth-abundant" elements. The principal targets in these efforts have been the first-row transition metals. Indeed, the groups of Chirik (5, 6), Morris (7), Beller (8), and others (9) have developed remarkably active and selective catalysts based on Fe.Strategies to develop reduction methods using organic or main-group-based reagents have also been explored. For example, use of Hantzsch esters (10), Birch reduction of arenes (11), or the use of B or Al hydrides are effective, albeit stoichiometric reductions. More recently, the advent of "frustrated Lewis pairs" (FLPs) have led to the discovery that combinations of sterically encumbered donors and acceptors act as catalysts for the reductions of imines, enamines, silylenol ethers, olefins, and alkynes (12).To uncover hydrogenation strategies using earth-abundant elements, we have focused our efforts on Lewis acidic phosphorus species. Although Gudat (13), Burford and coworker (14), Yoshifuji (15), and Bertrand and coworker (16), among others, have reported phosphenium cations that demonstrate Lewis acidity, Radosevich and coworkers (17) have exploited the reaction of the unique planar P(III) species with ammoniaborane to give a P(V)H 2 derivative that effects the subsequent reduction of diazobenzene. Although the acidity of P(V) has been exploited previously in ylide reagents (18), Diels-Alder reactions catalysis (19), and add...

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“…A significant departure from this approach is the use of dedicated robotic experimental systems, which could either involve parallel batch or flow experiments. Such systems are developed for high-throughput experiments and enable rapid discovery of new reactions [22,23,24 ], or optimization of process conditions of known reactions [25,26]. A flow array system has been used to discover a new inorganic cluster [7 ].…”

Section: Hardware For Self-optimization Of Closed-loop Systems Labwarementioning

confidence: 99%

Automatic discovery and optimization of chemical processes

Houben

Lapkin

2015

Current Opinion in Chemical Engineering

105

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This paper presents the first overview of recent developments in techniques and methods that enable closed-loop optimization, also sometimes called 'self optimization', as well as discovery in different areas of molecular sciences. The closed-loop experimental platforms offer tremendous new opportunities by significantly increasing productivity, as well as enabling completely new types of experiments to be performed. Such experiments involve three main enabling technology areas: automated experimental systems, analytical instruments connected to automated chemoinformatics software and optimization or decision-making algorithms. We review the most exciting developments concerning robotic experiments, 3D printed lab-ware, experimental systems with multiple analytical instruments and advanced optimization algorithms based on machine learning approaches. A range of different chemical problems is described, which show the breadth of potential applications of this emerging experimental approach.

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Cobalt Precursors for High-Throughput Discovery of Base Metal Asymmetric Alkene Hydrogenation Catalysts

Cited by 359 publications

References 42 publications

Exploiting Enzymatic Dynamic Reductive Kinetic Resolution (DYRKR) in Stereocontrolled Synthesis

Exploiting Enzymatic Dynamic Reductive Kinetic Resolution (DYRKR) in Stereocontrolled Synthesis

Metal-free transfer hydrogenation of olefins via dehydrocoupling catalysis

Automatic discovery and optimization of chemical processes

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