Non-equilibrium Steady States in Catalysis, Molecular Motors, and Supramolecular Materials: Why Networks and Language Matter

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(26), С. 14169 - 14183

Опубликована: Июнь 21, 2023

All chemists are familiar with the idea that, at equilibrium steady state, relative concentrations of species present in a system predicted by corresponding constants, which related to free energy differences between components. There is also no net flux species, matter how complicated reaction network. Achieving and harnessing non-equilibrium states, coupling network second spontaneous chemical process, has been subject work several disciplines, including operation molecular motors, assembly supramolecular materials, strategies enantioselective catalysis. We juxtapose these linked fields highlight their common features challenges as well some misconceptions that may be serving stymie progress.

Язык: Английский

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Stereodynamic Strategies to Induce and Enrich Chirality of Atropisomers at a Late Stage

Chemical Reviews, Год журнала: 2023, Номер 123(17), С. 10641 - 10727

Опубликована: Авг. 28, 2023

Enantiomers, where chirality arises from restricted rotation around a single bond, are atropisomers. Due to the unique nature of origins their chirality, synthetic strategies access these compounds in an enantioselective manner differ those used prepare enantioenriched containing point arising unsymmetrically substituted carbon center. In particular stereodynamic transformations, such as dynamic kinetic resolutions, thermodynamic and deracemizations, which rely on ability racemize or interconvert enantiomers, promising set transformations optically pure late stage sequence. Translation approaches with atropisomers requires expanded toolbox for epimerization/racemization provides opportunity develop new conceptual framework synthesis compounds.

Язык: Английский

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Kinetic Asymmetry and Directionality of Nonequilibrium Molecular Systems

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(9)

Опубликована: Янв. 18, 2024

Abstract Scientists have long been fascinated by the biomolecular machines in living systems that process energy and information to sustain life. The first synthetic molecular rotor capable of performing repeated 360° rotations due a combination photo‐ thermally activated processes was reported 1999. progress designing different intervening years has remarkable, with several outstanding examples appearing last few years. Despite accomplishments, there remains confusion regarding fundamental design principles which motions molecules can be controlled, significant intellectual tension between mechanical chemical ways thinking about describing machines. A thermodynamically consistent analysis kinetics rotors pumps shows while light driven operate power‐stroke mechanism, kinetic asymmetry—the relative heights barriers—is sole determinant directionality catalysis Power‐strokes—the depths wells—play no role whatsoever determining sign directionality. These results, elaborated using trajectory thermodynamics nonequilibrium pump equality, show asymmetry governs response many non‐equilibrium phenomena.

Язык: Английский

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Biocatalytic Enantioselective Synthesis of Atropisomers

Accounts of Chemical Research, Год журнала: 2022, Номер 55(23), С. 3362 - 3375

Опубликована: Ноя. 7, 2022

ConspectusAtropisomeric compounds are found extensively as natural products, ligands for asymmetric transition-metal catalysis, and increasingly bioactive pharmaceutically relevant targets. Their enantioselective synthesis is therefore an important ongoing research target. While a vast majority of known atropisomeric structures (hetero)biaryls, which display hindered rotation around C–C single bond, our group's long-standing interest in the control molecular conformation has led to identification stereoselective preparation variety other classes "nonbiaryl" displaying restricted C–C, C–N, C–O, C–S bonds.Biocatalytic transformations finding increasing application both academic industrial contexts result significant broadening range biocatalytic reactions sources enzymes available synthetic chemist. In this Account, we summarize main strategies currently biaryl, heterobiaryl, nonbiaryl atropisomers. As case with more traditional approaches these compounds, most methodologies construction enantioenriched atropisomers follow one two distinct strategies. The first direct bonds. Synthetically applicable type transformation limited, despite extensive into biosynthesis (hetero)biaryls by oxidative homocoupling or cross-coupling electron-rich arenes. second molecule bond that will form axis already exists, approach represents organic This strategy encompasses techniques including kinetic resolution (KR), desymmetrization, dynamic (DKR), (DYKAT).Nondynamic (KR) conformationally stable biaryl derivatives provided earliest numerous examples synthetically useful compounds. Lipases (i.e., mediate formation hydrolysis esters) particularly effective have attracted broad attention. success researchers broaden scope lipase-mediated desymmetrization reactions, addition limited number DKR DYKAT examples. By contrast, group used redox enzymes, engineered galactose oxidase (GOase) commercially ketoreductases (KREDs), desymmetrize prochiral diaryl ether derivatives. Building on experience conformational processes, later harnessed intramolecular noncovalent interactions facilitate at ambient temperatures, allowed development efficient heterobiaryl aldehydes using KREDs. With Account provide overview current prospective chemist molecules.

Язык: Английский

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Chemically Driven Rotatory Molecular Machines

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(40)

Опубликована: Июль 19, 2022

Molecular machines are at the frontier of biology and chemistry. The ability to control molecular motion emulating movement biological systems major steps towards development responsive adaptive materials. Amazing progress has been seen for design including light-induced unidirectional rotation overcrowded alkenes. However, feasibility inducing about a single bond as result chemical conversion challenging task. In this Review, an overview approaches design, synthesis, dynamic properties different classes atropisomers which can undergo controlled switching or under influence stimulus is presented. They categorized switches, rotors, motors, autonomous motors according their type response. Furthermore, we provide future perspective challenges focusing on building sophisticated machines.

Язык: Английский

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Photoactivated Artificial Molecular Motors

JACS Au, Год журнала: 2023, Номер 3(5), С. 1301 - 1313

Опубликована: Май 8, 2023

Accurate control of long-range motion at the molecular scale holds great potential for development ground-breaking applications in energy storage and bionanotechnology. The past decade has seen tremendous this area, with a focus on directional operation away from thermal equilibrium, giving rise to tailored man-made motors. As light is highly tunable, controllable, clean, renewable source energy, photochemical processes are appealing activate Nonetheless, successful motors fueled by challenging task, which requires judicious coupling photoinduced reactions. In paper, we key aspects light-driven artificial aid recent examples. A critical assessment criteria design, operation, technological such systems provided, along perspective view future advances exciting research area.

Язык: Английский

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Photoresponsive Biomimetic Functions by Light-Driven Molecular Motors in Three Dimensionally Printed Liquid Crystal Elastomers

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(20), С. 13894 - 13902

Опубликована: Май 10, 2024

Despite the fascinating developments in design and synthesis of artificial molecular machines operating at nanoscales, translating motion along multiple length scales inducing mechanical a three-dimensional macroscopic entity remains an important challenge. The key to addressing this amplification relies on effective organization well-defined environment. By taking advantage long-range orientational order hierarchical structures liquid crystals unidirectional rotation light-driven motors, we report here photoresponsive biomimetic functions crystal elastomers (LCEs) by repetitive motors using 3D printing. Molecular were built main chain oligomers serve as photoactuators. then used ink, with different morphologies printed. obtained LCEs are able conduct types motions including bending, helical coiling, closing petals, flipping wings butterfly upon UV illumination, which paves way for future responsive materials enhanced complex actuating functions.

Язык: Английский

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Stepwise Operation of a Molecular Rotary Motor Driven by an Appel Reaction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(7), С. 4467 - 4472

Опубликована: Фев. 6, 2024

To date, only a small number of chemistries and chemical fueling strategies have been successfully used to operate artificial molecular motors. Here, we report the 360° directionally biased rotation phenyl groups about C–C bond, driven by stepwise Appel reaction sequence. The motor molecule consists biaryl-embedded phosphine oxide phenol, in which full around biaryl bond is blocked P–O oxygen atom on rotor being too bulky pass stator. Treatment with SOCl2 forms cyclic oxyphosphonium salt (removing oxide), temporarily linking Conformational exchange via ring flipping then allows stator twist back forth past previous limit rotation. Subsequently, opening tethered intermediate chiral alcohol occurs preferentially through nucleophilic attack one face. Thus, original reformed net directional over course two-step Each repetition SOCl2–chiral additions generates another Using same sequence derivative that atropisomers rather than fully rotating results enantioenrichment, suggesting that, average, rotates "wrong" direction once every three cycles. interconversion oxides form temporary tethers enable rotational barrier be overcome adds available for generating chemically fueled kinetic asymmetry systems.

Язык: Английский

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Artificial molecular pumps

Nature Reviews Methods Primers, Год журнала: 2024, Номер 4(1)

Опубликована: Фев. 22, 2024

Язык: Английский

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Development of Configurationally Labile Biaryl Reagents for Atropisomer Synthesis

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(28)

Опубликована: Май 16, 2024

Abstract Axially chiral biaryl scaffolds are important in pharmaceuticals, natural products, and asymmetric synthesis. Atroposelective ring‐opening of configurationally labile reagents via dynamic kinetic transformation provides a valuable approach to access axially atropisomers. This review summarizes seminal contributions recent advancements on this topic based the use different types reagents.

Язык: Английский

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