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Topochemical reactions of monomers with conjugated triple bonds. III. Solid-state reactivity of derivatives of diphenyldiacetylene

1971

1972

Solid-state polymerization of monomers with conjugated triple bonds turns out to be a versatile method for synthesis of crystalline polymers of high molecular weight exhibiting a fully conjugated backbone. The reaction is best described as an 1.4-addition polymerization of the conjugated triple bonds giving rise to a polymer with three cumulated double bonds per repeating unit. The all-trans configuration of the substituents is a consequence of the solid-state reaction mechanism and is already predetermined by the packing of the molecules in the monomer lattice. It was shown by X-ray analysis in the case of poly(2.4-hexadiin-1.6-diol-bis-phenylurethane) that the polymer diacetylenes can be …

ChemInform Abstract: Catalytic Enantioselective Friedel-Crafts Reactions of Naphthols and Electron-Rich Phenols

2016

The enantioselective Friedel–Crafts reaction is a powerful tool for the construction of benzylic stereocenters in a stereodefined manner. Significant advances have already been achieved with heteroarenes such as indoles and pyrroles; however, the reaction with homoarenes is less developed. This short review covers the most relevant literature on enantioselective Friedel–Crafts reactions with naphthols and phenols. 1 Introduction 2 Friedel–Crafts Reactions Involving 1,2-Nucleophilic Addition to C=X Bonds 3 Friedel–Crafts Reactions Involving Conjugate Nucleophilic Addition to Electrophilic C=C Bonds 4 Friedel–Crafts Reactions Involving π-Allylic Complexes as Electrophiles 5 ipso-Friedel–Craft…

1971

Solid-state polymerization of the bis-(p-toluene sulfonate) of 2.4-hexadiin-1.6-diol was achieved by UV-irradiation or by annealing the monomer crystals below their melting-point. Deep red polymer crystals having the original shape of the monomer crystals exhibiting strong dichroism are obtained. Polymerization proceeds by 1.4-addition to the conjugated triple-bonds to form a polymer with three cumulated double bonds per baseunit and a fully conjugated backbone. Photopolymerization is rather fast and does not show an induction period. The relationship between ηsp/c-values and conversion as well as X-ray work indicates that the formation of nuclei must be an important feature of the reaction…

ChemInform Abstract: Highly Enantioselective Copper(I)-Catalyzed Conjugate Addition of Terminal Alkynes to 1,1-Difluoro-1-(phenylsulfonyl)-3-en-2-one…

2014

A highly enantioselective copper-catalyzed conjugate alkynylation of monoactivated enones, namely 1,1-difluoro-1-(phenylsulfonyl)-3-en-2-ones, is described. The reaction products are obtained with good yields and excellent enantioselectivities (from 92 to 99% ee). The β-alkynylated difluoro(phenylsulfonyl) ketones can be converted into the corresponding β-alkynylated difluoro- and trifluoromethyl ketones, esters and amides. This is the first example on the use of 1,1-difluoro-1-(phenylsulfonyl)-3-en-2-ones as substrates in an enantioselective reaction, which have been shown to be new ester/amide surrogates.

ChemInform Abstract: Catalytic Enantioselective Conjugate Alkynylation of α,β-Unsaturated 1,1,1-Trifluoromethyl Ketones with Terminal Alkynes.

2016

Financial support (Grant CTQ2013-47494-P) from the Ministerio de Economia y Competitividad (MINECO-Gobierno de Espana). A.S.M. thanks the MINECO for a predoctoral grant (FPI program). Access to NMR and MS facilities from the Servei Central de Suport a la Investigacio Experimental (SCSIE)-UV is also acknowledged.

ChemInform Abstract: Catalytic Asymmetric Conjugate Addition of Terminal Alkynes to β-Trifluoromethyl α,β-Enones.

2014

The first enantioselective conjugate alkynylation of β-trifluoromethyl α,β-enones (II) using terminal alkynes (I) and a taniaphos-Cu(I) complex as catalyst is described.

ChemInform Abstract: Catalytic Enantioselective Conjugate Alkynylation of β-Aryl-β-trifluoromethyl Enones Constructing Propargylic All-Carbon Quatern…

2016

The enantioselective conjugate alkynylation of β-aryl-β-trifluoromethyl enones has been carried out using terminal alkynes and diethylzinc in the presence of 3,3′-bis(perfluorophenyl)BINOL as the chiral ligand to give the corresponding ketones bearing a trifluoromethylated propargylic quaternary stereocenter with fair to good enantioselectivities. Enones bearing a bulky 2-naphthyl attached to the carbonyl group provided the best enantioselectivities. The synthetic applicability of the resulting products has been demonstrated with their iodocyclization to form 4H-pyrans.

Generation of hexahydroazulenes

2009

(Z)-Cyclodec-1-en-6-yne (3) generates three conjugated hexahydroazulenes 3→1k→1c, 1l under FVP conditions, whereas flash vacuum pyrolysis (FVP) of cyclodecyne (2) leads to 1,2,9-decatriene (9). We attribute the different thermal behavior of 2 (ring opening) and 3 (ring closure) to different transannular interactions. Altogether 22 constitutional isomers of hexahydroazulene should exist; three new isomers (1k, 1l, and 1m) are presented here, ten were described earlier, but the reinvestigation of the dehydration route of bicyclic alcohol 11 showed that one of the ten structures has to be revised.

Enantioselective Synthesis of 2-Isoxazolines by a One-Flask Conjugate Addition/Oxime-Transfer Process

2009

Enantioselective isoxazoline synthesis: A combination of 1) a catalytic enantioselective conjugate addition of oximes to alpha,beta-unsaturated aldehydes and 2) an acid-catalyzed intramolecular oxime-transfer reaction lead to the first asymmetric synthesis of 3-unsubstituted 2-isoxazolines (see scheme).