Stereoselective Synthesis of Bicyclo[3.1.1]Heptane Derivatives via Intramolecular Photocycloaddition Reaction

Honda, Kiyoshi; Konishi, Mari; Kawai, Manabu; Yamada, Akihisa; Takahashi, Yasuhiko; Hoshino, Yujiro; Inoue, Seiichi

doi:10.1177/1934578x1200700410

Cited by 2 publications

(1 citation statement)

References 30 publications

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“…Chemical reactions initiated by the absorption of a photon are at the core of organic synthesis, 1 catalysis, 2 optogenetics, 3 protein modification, 4 conversion, and storage of solar energy 5 and hold promise for many other applications. 6 While many photochemical reactions are ultrafast and occur on a femtosecond time scale, 7 high barriers on electronically excited potential energy surfaces (PESs) or nonadiabatic transitions 8 with small couplings may lead to much slower reactions.…”

Section: Introductionmentioning

confidence: 99%

Nonadiabatic Forward Flux Sampling for Excited-State Rare Events

Reiner

Bachmair

Tiefenbacher

et al. 2023

J. Chem. Theory Comput.

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We present a rare event sampling scheme applicable to coupled electronic excited states. In particular, we extend the forward flux sampling (FFS) method for rare event sampling to a nonadiabatic version (NAFFS) that uses the trajectory surface hopping (TSH) method for nonadiabatic dynamics. NAFFS is applied to two dynamically relevant excited-state models that feature an avoided crossing and a conical intersection with tunable parameters. We investigate how nonadiabatic couplings, temperature, and reaction barriers affect transition rate constants in regimes that cannot be otherwise obtained with plain, traditional TSH. The comparison with reference brute-force TSH simulations for limiting cases of rareness shows that NAFFS can be several orders of magnitude cheaper than conventional TSH and thus represents a conceptually novel tool to extend excited-state dynamics to time scales that are able to capture rare nonadiabatic events.

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Section: Introductionmentioning

confidence: 99%

Nonadiabatic Forward Flux Sampling for Excited-State Rare Events

Reiner

Bachmair

Tiefenbacher

et al. 2023

J. Chem. Theory Comput.

View full text Add to dashboard Cite

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Selective [2σ + 2σ] Cycloaddition Enabled by Boronyl Radical Catalysis: Synthesis of Highly Substituted Bicyclo[3.1.1]heptanes

Yang

Wang

et al. 2023

J. Am. Chem. Soc.

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In contrast to the traditional and widely-used cycloaddition reactions involving at least a π bond component, a [2σ + 2σ] radical cycloaddition between bicyclo[1.1.0]butanes (BCBs) and cyclopropyl ketones has been developed to provide a modular, concise, and atom-economical synthetic route to substituted bicyclo[3.1.1]heptane (BCH) derivatives that are 3D bioisosteres of benzenes and core skeleton of a number of terpene natural products. The reaction was catalyzed by a combination of simple tetraalkoxydiboron(4) compound B 2 pin 2 and 3-pentyl isonicotinate. The broad substrate scope has been demonstrated by synthesizing a series of new highly functionalized BCHs with up to six substituents on the core with up to 99% isolated yield. Computational mechanistic investigations supported a pyridine-assisted boronyl radical catalytic cycle.

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Stereoselective Synthesis of Bicyclo[3.1.1]Heptane Derivatives via Intramolecular Photocycloaddition Reaction

Cited by 2 publications

References 30 publications

Nonadiabatic Forward Flux Sampling for Excited-State Rare Events

Nonadiabatic Forward Flux Sampling for Excited-State Rare Events

Selective [2σ + 2σ] Cycloaddition Enabled by Boronyl Radical Catalysis: Synthesis of Highly Substituted Bicyclo[3.1.1]heptanes

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