Indole(NH3)n clusters: hydrogen atom transfer initiated by femtosecond laser pulses

2002 ◽  
Author(s):  
V. Stert ◽  
L. Hesse ◽  
H. Lippert ◽  
C. P. Schulz ◽  
W. Radloff
Keyword(s):  
Hydrogen Atom ◽  
Femtosecond Laser ◽  
Laser Pulses ◽  
Femtosecond Laser Pulses ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer

Inorganic-organic Hybrid Materials for Real 3-D Sub-νm Lithography

2003 ◽  
Vol 780 ◽  
Author(s):  
R. Houbertz ◽  
J. Schulz ◽  
L. Fröhlich ◽  
G. Domann ◽  
M. Popall ◽  
...  
Keyword(s):  
Femtosecond Laser ◽  
Sol Gel ◽  
Laser Pulses ◽  
Femtosecond Laser Pulses ◽  
Hybrid Polymer ◽  
Organic Hybrid ◽  
Two Photon ◽  
Applied Technology ◽  
Scale Structures ◽  
Sol Gel Synthesis

AbstractReal 3-D sub-νm lithography was performed with two-photon polymerization (2PP) using inorganic-organic hybrid polymer (ORMOCER®) resins. The hybrid polymers were synthesized by hydrolysis/polycondensation reactions (modified sol-gel synthesis) which allows one to tailor their material properties towards the respective applications, i.e., dielectrics, optics or passivation. Due to their photosensitive organic functionalities, ORMOCER®s can be patterned by conventional photo-lithography as well as by femtosecond laser pulses at 780 nm. This results in polymerized (solid) structures where the non-polymerized parts can be removed by conventional developers.ORMOCER® structures as small as 200 nm or even below were generated by 2PP of the resins using femtosecond laser pulses. It is demonstrated that ORMOCER®s have the potential to be used in components or devices built up by nm-scale structures such as, e.g., photonic crystals. Aspects of the materials in conjunction to the applied technology are discussed.

Ablation of metals with femtosecond laser pulses

2001 ◽  
Author(s):  
K. H. Leong ◽  
T. Y. Plew ◽  
R. L. Maynard ◽  
A. A. Said ◽  
L. A. Walker
Keyword(s):  
Femtosecond Laser ◽  
Laser Pulses ◽  
Femtosecond Laser Pulses

Direct Cyclization of Alkenyl Thioester via Transition Metal‐hydrogen Atom Transfer/radical‐polar Crossover Mechanism

2019 ◽  
Author(s):  
Shiori Date ◽  
Kensei Hamasaki ◽  
Karen Sunagawa ◽  
Hiroki Koyama ◽  
Chikayoshi Sebe ◽  
...  
Keyword(s):  
Natural Products ◽  
Hydrogen Atom ◽  
Transition Metal ◽  
Hydrogen Atom Transfer ◽  
Synthetic Method ◽  
Atom Transfer ◽  
Reaction Conditions ◽  
Hydride Hydrogen ◽  
Sulfur Heterocycles ◽  
One Step

<div>We report here a catalytic, Markovnikov selective, and scalable synthetic method for the synthesis of saturated sulfur heterocycles, which are found in the structures of pharmaceuticals and natural products, in one step from an alkenyl thioester. Unlike a potentially labile alkenyl thiol, an alkenyl thioester is stable and easy to prepare. The powerful Co catalysis via a cobalt hydride hydrogen atom transfer and radical-polar crossover mechanism enabled simultaneous cyclization and deprotection. The substrate scope was expanded by the extensive optimization of the reaction conditions and tuning of the thioester unit.</div>

Catalytic Synthesis of Cyclic Guanidines via Hydrogen Atom Transfer and Radical-Polar Crossover

2020 ◽  
Author(s):  
Shunya Ohuchi ◽  
Hiroki Koyama ◽  
Hiroki Shigehisa
Keyword(s):  
Hydrogen Atom ◽  
Functional Group ◽  
Hydrogen Atom Transfer ◽  
Catalytic Synthesis ◽  
Membered Ring ◽  
Biologically Active ◽  
Atom Transfer ◽  
Powerful Method ◽  
Protective Groups ◽  
The Common

A catalytic synthesis of cyclic guanidines, which are found in many biologically active compounds and natu-ral products, was developed, wherein transition-metal hydrogen atom transfer and radical-polar crossover were employed. This mild and functional-group tolerant process enabled the cyclization of alkenyl guanidines bearing common protective groups, such as Cbz and Boc. This powerful method not only provided the common 5- and 6-membered rings but also an unusual 7-membered ring. The derivatization of the products afforded various heterocycles. We also investigated the se-lective cyclization of mono-protected or hetero-protected (TFA and Boc) alkenyl guanidines and their further derivatiza-tions.

Sulfamides Direct Radical-Mediated Chlorination of Aliphatic C–H Bonds

2019 ◽  
Author(s):  
Melanie Short ◽  
Mina Shehata ◽  
Matthew Sanders ◽  
Jennifer Roizen
Keyword(s):  
Hydrogen Atom ◽  
Transfer Reaction ◽  
Hydrogen Atom Transfer ◽  
Chain Propagation ◽  
Propagation Mechanism ◽  
Atom Transfer ◽  
Radical Chain ◽  
Radical Intermediates ◽  
Transfer Processes ◽  
Unusual Position

Sulfamides guide intermolecular chlorine transfer to gamma-C(sp<sup>3</sup>) centers. This unusual position-selectivity arises because accessed sulfamidyl radical intermediates engage in otherwise rare 1,6-hydrogen-atom transfer processes. The disclosed chlorine-transfer reaction relies on a light-initiated radical chain-propagation mechanism to oxidize C(sp<sup>3</sup>)-H bonds.

Sulfamides Direct Radical-Mediated Chlorination of Aliphatic C–H Bonds

2019 ◽  
Author(s):  
Melanie Short ◽  
Mina Shehata ◽  
Matthew Sanders ◽  
Jennifer Roizen
Keyword(s):  
Hydrogen Atom ◽  
Transfer Reaction ◽  
Hydrogen Atom Transfer ◽  
Chain Propagation ◽  
Propagation Mechanism ◽  
Atom Transfer ◽  
Radical Chain ◽  
Radical Intermediates ◽  
Transfer Processes ◽  
Unusual Position

Sulfamides guide intermolecular chlorine transfer to gamma-C(sp<sup>3</sup>) centers. This unusual position-selectivity arises because accessed sulfamidyl radical intermediates engage in otherwise rare 1,6-hydrogen-atom transfer processes. The disclosed chlorine-transfer reaction relies on a light-initiated radical chain-propagation mechanism to oxidize C(sp<sup>3</sup>)-H bonds.

Hydrogen Atom Transfer Reaction Free Energy as a Predictor of Abiotic Nitroaromatic Reduction Rate Constants: A Comprehensive Analysis

2019 ◽  
Author(s):  
Dominic Di Toro ◽  
Kevin P. Hickey ◽  
Herbert E. Allen ◽  
Richard F. Carbonaro ◽  
Pei C. Chiu
Keyword(s):  
Free Energy ◽  
Hydrogen Atom ◽  
Hydrogen Atom Transfer ◽  
Energy Model ◽  
Second Order ◽  
Transfer Model ◽  
Atom Transfer ◽  
Order Rate ◽  
Linear Free Energy ◽  
Free Energy Model

<div>A linear free energy model is presented that predicts the second order rate constant for the abiotic reduction of nitroaromatic compounds (NACs). For this situation previously presented models use the one electron reduction potential of the NAC reaction. If such value is not available, it has been has been proposed that it could be computed directly or estimated from the electron affinity (EA). The model proposed herein uses the Gibbs free energy of the hydrogen atom transfer (HAT) as the parameter in the linear free energy model. Both models employ quantum chemical computations for the required thermodynamic parameters. The available and proposed models are compared using second order rate constants obtained from five investigations reported in the literature in which a variety of NACs were exposed to a variety of reductants. A comprehensive analysis utilizing all the NACs and reductants demonstrate that the computed hydrogen atom transfer model and the experimental one electron reduction potential model have similar root mean square errors and residual error probability distributions. In contrast, the model using the computed electron affinity has a more variable residual error distribution with a significant number of outliers. The results suggest that a linear free energy model utilizing computed hydrogen transfer reaction free energy produces a more reliable prediction of the NAC abiotic reduction second order rate constant than previously available methods. The advantages of the proposed hydrogen atom transfer model and its mechanistic implications are discussed as well.</div>

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