Publications related to Allenes

The fundamental relation between electrohelicity and molecular optical activity

Anne-Clémence Corminboeuf, Marc Hamilton Folkmann Garner

Electrohelicity arises in molecules such as allene and spiropentadiene when their symmetry is reduced and helical frontier molecular orbitals (MOs) appear. Such molecules are optically active and electrohelicity has been suggested as a possible design prin ...

ROYAL SOC CHEMISTRY2023

Development of Hetero-Vinylbenziodoxolone Reagents for Applications in Synthetic Methodology and Biomolecule Functionalization

Nina Declas

Among the numerous existing chemical motifs, alkenes, alkynes, enol ethers and enamides, with an unsaturated carbon-carbon bond, are versatile functional groups that are found in many natural products and bioactive compounds. They are widely used as valuab ...

EPFL2023

Radical Alkynylations with EthynylBenziodoXolones: From Photocatalysis to Direct Excitation

Jérôme Waser, Stephanie Grace Elizabeth Amos

Ethynylbenziodoxolones (EBXs) have recently emerged as potent reagents for the alkynylation of radicals. Their combination with photocatalysis allows the synthesis of valuable alkynes at room temperature. Herein, we discuss two photomediated strategies for ...

2022

Enantio- and diastereoselective construction of vicinal C(sp(3)) centres via nickel-catalysed hydroalkylation of alkenes

Xile Hu, Chao Fan, Srikrishna Bera

In drug discovery, the proportion of aliphatic carbons (C(sp(3))) and the presence of chiral carbons in organic molecules are positively correlated to their chance of clinical success. Although methods exist for the synthesis of chiral C(sp(3))-rich molecu ...

2022

Helical electronic transitions of spiroconjugated molecules

Anne-Clémence Corminboeuf, Marc Hamilton Folkmann Garner

The two pi-systems of allene can combine into helical molecular orbitals (MOs), yet the helicity is lost in the pi-pi* transitions due to excited state mixing. In spiroconjugated molecules the relative orientation of the two pi-systems is different and con ...

Royal Society of Chemistry2021

Correlation between Optical Activity and the Helical Molecular Orbitals of Allene and Cumulenes

Anne-Clémence Corminboeuf, Marc Hamilton Folkmann Garner

Helical frontier molecular orbitals (MOs) appear in disubstituted allenes and even-n cumulenes. Chiral molecules are optically active, but while these molecules are single-handed chiral, p-orbitals of both helicities are present. Here we computationally ex ...

AMER CHEMICAL SOC2020

Palladium Catalysed Intramolecular Carbo-oxygenation of Propargylic Amines to Access 1,2-Amino Alcohols and alpha-Amino Ketones via in situ Tether Formation

Phillip Gulliver Dominic Greenwood

a-Amino ketones and 1,2-amino alcohols are important structural motifs in organic chemistry, that can be observed in natural products, pharmaceutically and bioactive compounds. For these reasons, they constitute privileged targets for the development of ne ...

EPFL2020

Nickel-Catalyzed Regioselective Hydroalkylation and Hydroarylation of Alkenyl Boronic Esters

Xile Hu, Srikrishna Bera

Metal hydride catalyzed hydrocarbonation reactions of alkenes are an efficient approach to construct new carbon-carbon bonds from readily available alkenes. However, the regioselectivity of hydrocarbonation remains challenging to be controlled. In nickel h ...

Wiley-VCH Verlag GmbH2019

Metal-Free Electrophilic Alkynylation of Sulfenate Anions with Ethynylbenziodoxolone Reagents

Jérôme Waser, Stefano Nicolai, Franck Le Vaillant, Alec Gagnebin, Stephanie Grace Elizabeth Amos

Alkynyl sulfoxides are important building blocks with a unique reactivity in organic chemistry, but only a few reliable methods have been reported to synthesize them. A novel route to access alkynyl sulfoxides is reported herein by using ethynyl benziodoxo ...

2019

Investigations of the Chemistry of 1-Alkynyltriazenes

Florian Gérald Abela

The chemistry of aromatic triazenes is well known, and has been explored for more than a century. These compounds have emerged as very useful intermediates, because of their unique reactivity. This functionality can notably be used to access many other fun ...

EPFL2018

Mild synthesis of mercaptonitriles from vinyl nitriles and their cyclization reactions

Frank Nüesch, Antonia Neels

Thiol-ene addition of thioacetic acid A is widely used in the synthesis of thiols from vinyl precursors, but so far has not been conducted on non-conjugated vinyl nitriles. The challenge when vinyl nitriles are used is to selectively conduct the thiol-ene ...

Royal Soc Chemistry2016

Rh(III)-Catalyzed C-H Functionalizations as Strategies for Versatile Organic Building Blocks

Van Manh Pham

Transition-metal catalyzed C-H functionalizations have impacted and changed synthetic approaches towards the construction of relevant complex molecules, comprising natural products, active pharmaceutical ingredients, and organic materials. This thesis desc ...

EPFL2016

Synthesis of Alkynylated Heterocycles by Direct C-H Alkynylation or Domino Alkynylation Reactions

Yifan Li

Heterocycles are important compounds in organic chemistry. To introduce functional groups on heterocycles or synthesize functionalized heterocycles stays a hot topic of research. Among all the functional groups, alkynes attracted a lot of attention not onl ...

EPFL2016

Stereoselective Synthesis of Trisubstituted Alkenes through Sequential Iron-Catalyzed Reductive anti-Carbozincation of Terminal Alkynes and Base-Metal-Catalyzed Negishi CrossCoupling

Xile Hu, Chi Wai Cheung

The stereoselective synthesis of trisubstituted alkenes is challenging. Here, we show that an iron-catalyzed anti-selective carbozincation of terminal alkynes can be combined with a base-metal-catalyzed cross coupling to prepare trisubstituted alkenes in a ...

Wiley-Blackwell2015

Cryogenic Spectroscopy and Quantum Molecular Dynamics Determine the Structure of Cyclic Intermediates Involved in Peptide Sequence Scrambling

Ursula Röthlisberger, Thomas Rizzo, Oleg Aseev, Marta Andreia Da Silva Perez

Collision-induced dissociation (CID) is a key technique used in mass spectrometry-based peptide sequencing. Collisionally activated peptides undergo statistical dissociation, forming a series of backbone fragment ions that reflect their amino acid (AA) seq ...

2015

Intricacies of Describing Weak Interactions involving Halogen Atoms within Density Functional Theory

Ursula Röthlisberger, Ivano Tavernelli, Manuel Dömer

In this work we assess the performance of different dispersion-corrected DFT approaches (M06, M06-2X, DFT-D3 and DCACP) in reproducing high-level wave function based benchmark calculations on the weakly bound halogen dimers (X2)2 and X2-Ar (for X=F,Cl,Br,I ...

Amer Chemical Soc2013

Heteroatom Nucleophile Induced C-C Fragmentations to Access Functionalized Allenes

Nicolai Cramer, Tanguy Jean Daniel Saget

The rich structural and reactivity profile of allenes render them versatile synthetic intermediates. However, application of allenes in organic chemistry is often attenuated by inconvenient methods of preparation. Herein we present an operationally simple ...

2012

Design and Development of Functionalized Cyclometalated Ruthenium Chromophores for Light-Harvesting Applications

Michael Graetzel, Mohammad Khaja Nazeeruddin, Aswani Yella, Thomas Baumgartner

The syntheses and the electrochemical spectroscopic properties of a suite of asymmetrical bistridentate cyclometalated Ru(II) complexes bearing terminal triphenylamine (TPA) substituents are reported. These complexes, which contain structural design elemen ...

2011

The biphenyl-monitored effective size of unsaturated functional or fluorinated ortho substituents

The size of a series of typical substituents has been probed by dynamic NMR measurements of the barriers to aryl-aryl rotation of the corresponding biphenyls. The resulting B values are meaningful because only mono-ortho substituted compounds were investig ...

2010

Stacking and spreading interaction in N-heteroaromatic systems

Jeremy Samuel Arey, Brijesh Kumar Mishra

π−π interactions in heteroaromatic systems are ubiquitous in biological systems. In the present study, stabilization energies of stacked and hydrogen-bonded dimers of N-heteroaromatic systems (pyridine, pyrazine, sym-triazine, and sym-tetrazine) have been ...

American Chemical Society2010