Data-Driven Models for Predicting Intrinsically Disordered Protein Polymer Physics Directly from Composition or Sequence.

The molecular-level understanding of intrinsically disordered proteins is challenging due to experimental characterization difficulties. Computational understanding of IDPs also requires fundamental advances, as the leading tools for predicting protein folding (e.g.

Examination of the Brønsted-Evans-Polanyi relationship for the hydrogen evolution reaction on transition metals based on constant electrode potential density functional theory.

In the search for efficient and inexpensive electrocatalysts for the hydrogen evolution reaction (HER), the hydrogen binding energy is often used as a descriptor to represent the catalytic activity. The success of this approach relies on the Brønsted-Evans-Polanyi (BEP) relationship. In this study, we used constant electrode potential density functional theory calculations to examine this relationship.

Copper-catalyzed carbo-difluoromethylation of alkenes via radical relay.

Organic molecules that contain alkyl-difluoromethyl moieties have received increased attention in medicinal chemistry, but their synthesis in a modular and late-stage fashion remains challenging. We report herein an efficient copper-catalyzed radical relay approach for the carbo-difluoromethylation of alkenes. This approach simultaneously introduces CFH groups along with complex alkyl or aryl groups into alkenes with regioselectivity opposite to traditional CFH radical addition.

First-Principles Evaluation of One-Dimensional Metal-Organic Frameworks for Electrocatalytic C-H Activation of Natural Gas.

To replace the oxygen evolution reaction with thermodynamically more favorable and economically more profitable methane and ethane (the major components of natural gas) electrochemical partial oxidation, we employed constant electrode potential density functional theory calculations to screen 20 one-dimensional metal-organic frameworks containing heteroatom-substituted benzene as electrocatalysts. By computing the Pourbaix diagrams, O-H binding energies, and C-H activation barriers, we determined that although none of these catalysts were able to activate methane, one was able to hydroxylate ethane to ethanol with facile kinetics, making it a promising electrocatalyst for natural gas oxidation.

Gold-Catalyzed [3+2]-Annulations of α-Aryl Diazoketones with the Tetrasubstituted Alkenes of Cyclopentadienes: High Stereoselectivity and Enantioselectivity.

This work reports gold-catalyzed [3+2]-annulations of α-diazo ketones with highly substituted cyclopentadienes, affording bicyclic 2,3-dihydrofurans with high regio- and stereoselectivity. The reactions highlights the first success of tetrasubstituted alkenes to undergo [3+2]-annulations with α-diazo carbonyls. The enantioselective annulations are also achieved with high enantioselectivity using chiral forms of gold and phosphoric acid.

[2,2](5,8)Picenophanedienes: Syntheses, Structural Analyses, Molecular Dynamics, and Reversible Intramolecular Structure Conversion.

This study presents an important and efficient synthetic approach to 5,8-dibromo-2,11-dibutylpicene (), with multigram scale, which was then converted to a new series of picenophanes (-). The tub-shaped [2,2](5,8)picenophanediene with two -ethylene linkers was explored using X-ray crystallography. The tub-to-tub inversion proceed through the successive bending of the linkers and the barrier for isopropyl-substituted derivative was experimentally estimated to be 18.

Gold-Catalyzed Oxidative Aminocyclizations of Propargyl Alcohols and Propargyl Amines to Form Two Distinct Azacyclic Products: Carbene Formation versus a 3,3-Sigmatropic Shift of an Initial Intermediate.

Gold-catalyzed oxidations of propargyl alcohols with nitrones by using a P(tBu) (o-biphenyl)Au catalyst, afforded bicyclic annulation products from the Mannich reactions of gold enolates. The same reactions of propargyl amines with nitrones by using the same gold catalyst gave distinct oxoarylation products. Our DFT calculations indicate that oxidation of propargyl alcohols with nitrones by using electron-rich gold catalysts lead only to gold carbenes, which can generate gold enolates or oxoarylation intermediates with enolate species having a barrier smaller than that of oxoarylation species.

Gold(I)-Catalyzed Highly Diastereo- and Enantioselective Cyclization-[4+3] Annulation Cascades between 2-(1-Alkynyl)-2-alken-1-ones and Anthranils.

This work reports gold-catalyzed [4+3]-annulations of 2-(1-alkynyl)-2-alken-1-ones with anthranils to yield epoxybenzoazepine products with excellent exo-diastereoselectivity (dr>25:1). The utility of this new gold catalysis is manifested by applicable substrates over a broad scope. More importantly, the enantioselective versions of these [4+3]-cycloadditions have been developed satisfactorily with chiral gold catalysts under ambient conditions (DCM, 0 °C); the ee levels range from 88.

Copper-Catalyzed Decarboxylative Difluoromethylation.

We report herein a highly efficient Cu-catalyzed protocol for the conversion of aliphatic carboxylic acids to the corresponding difluoromethylated analogues. This robust, operationally simple and scalable protocol tolerates a variety of functional groups and can convert a diverse array of acid-containing complex molecules to the alkyl-CFH products. Mechanistic studies support the involvement of alkyl radicals.