Environmentally responsible, safe, and chemoselective catalytic hydrogenation of olefins: ppm level Pd catalysis in recyclable water at room temperature

Takale, Balaram S.; Thakore, Ruchita R.; Gao, Eugene S.; Gallou, Fabrice; Lipshutz, Bruce H.

doi:10.1039/d0gc02087g

Cited by 31 publications

(15 citation statements)

References 36 publications

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“…These tandem, mixed bio- and chemo-catalysis sequences are not limited to two steps. As shown in Scheme 5 , catalytic hydrogenation of cinnamic acid 44 in water in the presence of the Pd/C 27 led to intermediate acid 20. Subsequent lipase-catalyzed esterification with alcohol 45 gave gem -dibromocyclopropane 46, which was then reduced by nickel nanoparticles 28 to give product 47 in 65% overall isolated yield, all done, sequentially, in water.…”

Section: Resultsmentioning

confidence: 99%

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Lipase-catalyzed esterification in water enabled by nanomicelles. Applications to 1-pot multi-step sequences

et al. 2022

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Section: Resultsmentioning

confidence: 99%

“…Pd-catalyzed Suzuki-Miyaura vinylation to 55, and thence olefin reduction27 to arrive at ester 56. It is worthy of note that the first, selective enzymatic step takes place without protecting group chemistry (of the indole), in further alignment with the 12 Principles of Green Chemistry 32,33.…”

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Lipase-catalyzed esterification in water enabled by nanomicelles. Applications to 1-pot multi-step sequences

et al. 2022

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“…High school students are getting trained over the summer in our labs, and with proper guidance, have been remarkably responsive. 69,70 We are also in the process of using our decade-plus of experience with so many important reactions now doable in water to create an undergraduate lab Manual that will bring the same level of pedagogy to sophomore organic labs, but with experiments (e.g., click reactions, nitro group reductions, Pd-catalyzed couplings, etc.) that rely totally on chemistry in water.…”

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confidence: 99%

Illuminating a Path4914. Copyright 2016 Wiley for Organic Synthesis Towards Sustainability. No One Said It Would Be Easy…

Lipshutz¹

2021

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A personalized account is presented describing some of the stories behind the scenes in efforts to convert organic chemistry into a more sustainable discipline. These are part of a group ‘crusade’ started almost 15 years ago aimed at providing technologies illustrative of how key reactions used today can be ‘faster, better, cheaper’ when run in recyclable water. Hence, the option now exists to do organic synthesis in a far more environmentally responsible fashion. By contrast, most of organic chemistry developed over the past 200 years that relies on organic solvents continues to generate enormous amounts of pollution, while depleting finite petroleum reserves and our supplies of many precious and base metals. Making the switch to water, Nature’s chosen reaction medium, akin to that in which bio-catalysis is typically performed, is inevitable.1 The Story Begins: A Different Type of Prejudice2 Are We up to the Challenge? Too Late Now…3 ‘Impossible’ Reactive Metal Chemistry in Water4 Didn’t I Once Say: ‘It’s All about the Ligand’?5 What Happens When Our Supply of Palladium Runs Out?6 What Are the Implications from These Tales for Today and Tomorrow?7 What Is the ‘Broader Impact’ of This Work?8 The Bottom Line…

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“…We therefore investigated the application of micellar methodology to on‐DNA hydrogenation using catalytic hydrogen transfer. Encouragingly, catalytic hydrogenation using micelle forming surfactants with hydrogen gas has been recently reported [17–19] . It has been shown that TPGS‐750‐M derived micelles can associate with metal surfaces in aqueous systems [20] and that the surfactant MC‐1 associates with palladium on carbon [21] .…”

Section: Figurementioning

confidence: 99%

On‐DNA Transfer Hydrogenolysis and Hydrogenation for the Synthesis of DNA‐Encoded Chemical Libraries

2021

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DNA‐encoded libraries (DELs) are an increasingly popular approach to finding small molecule ligands for proteins. Many DEL synthesis protocols hinge on sequential additions of monomers using split‐pool combinatorial methods. Therefore, compatible protecting group strategies that allow the unmasking of reactive functionality (e. g. amines and alcohols) prior to monomer coupling, or the removal of less desirable functionality (e. g., alkenes and alkynes) are highly desirable. Hydrogenation/hydrogenolysis procedures would achieve these ends but have not been amenable to DEL chemistry. We report a catalytic hydrogen transfer reaction using Pd/C, HCONH4 and the micelle‐forming surfactant, TPGS‐750‐M, which gives highly efficient conversions for hydrogenolysis of Cbz‐protected amines and benzyl protected alcohols and hydrogenation of nitros, halides, nitriles, aldehydes, alkenes and alkynes. Application to multicycle synthesis of an encoded compound was fully compatible with DNA‐amplification and sequencing, demonstrating its applicability to DEL synthesis. This method will enable synthetic DEL sequences using orthogonal protecting groups.

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Environmentally responsible, safe, and chemoselective catalytic hydrogenation of olefins: ppm level Pd catalysis in recyclable water at room temperature

Abstract: Textbook catalytic hydrogenations are typically presented as reactions done in organic solvents and oftentimes under varying pressures of hydrogen using specialized equipment.

Cited by 31 publications

References 36 publications

Lipase-catalyzed esterification in water enabled by nanomicelles. Applications to 1-pot multi-step sequences

Lipase-catalyzed esterification in water enabled by nanomicelles. Applications to 1-pot multi-step sequences

Illuminating a Path4914. Copyright 2016 Wiley for Organic Synthesis Towards Sustainability. No One Said It Would Be Easy…

On‐DNA Transfer Hydrogenolysis and Hydrogenation for the Synthesis of DNA‐Encoded Chemical Libraries

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