Control of nanostructures in epoxy/acrylic block copolymer blends by the in situ generation of functional groups

Aryl diazonium ions are useful across a range of chemical/biochemical areas. These species are generally made using strongly acidic conditions, which can be detrimental to acid-sensitive functional groups. The ability to generate benzene diazonium ions under basic aqueous conditions is reported herein along with newfound understanding on the aqueous reactivity of solubilized triazabutadienes whereby π-interactions appear to confer a large degree of stability.

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An I(I)/I(III) Catalysis Route to the Heptafluoroisopropyl Group: A Privileged Module in Contemporary Agrochemistry

Synthesis ◽

10.1055/a-1485-4916 ◽

2021 ◽

Author(s):

Victor Martín-Heras ◽

Constantin G. Daniliuc ◽

Ryan Gilmour

Keyword(s):

Functional Groups ◽

Hypervalent Iodine ◽

Aryl Ring ◽

Iodine Species ◽

Single Operation ◽

Group A ◽

Molecule Design ◽

In Situ Generation

The heptafluoroisopropyl group is emerging as a privileged chemotype in contemporary agrochemistry and features prominently in the current portfolio of leading insecticides. To reconcile the expansive potential of this module with the synthetic challenges associated with preparing crowded, fluorinated motifs, I(I)/I(III) catalysis has been leveraged. Predicated on in situ generation of p-TolIF2, this route enables the direct difluorination of α-trifluoromethyl-β-difluoro-styrenes in a single operation. This formal addition of fluorine across the alkene π-bond is efficient (up to 91%) and is compatible with a broad range of functional groups. The ArCF(CF3)2 moiety is conformationally pre-organized, with the C(sp3)-F bond co-planar to the framework of the aryl ring, thereby minimizing 1,3-allylic strain. Moreover, orthogonal multipolar C-F•••C=O interactions have been identified in a phathalimide derivative. It is envisaged that this programmed vicinal difluorination enabled by a hypervalent iodine species will find application in functional molecule design in a broader sense.

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Peel Adhesive Properties of Epoxy / Acrylic Block Copolymer Blends;Effect of in-situ Formed Nanophase Structures

Journal of The Adhesion Society of Japan ◽

10.11618/adhesion.53.296 ◽

2017 ◽

Vol 53 (9) ◽

pp. 296-302

Author(s):

YAMADA Kazuyoshi ◽

Hajime KISHI

Keyword(s):

Block Copolymer ◽

Adhesive Properties ◽

Copolymer Blends

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Control of nanostructures and fracture toughness of epoxy/acrylic block copolymer blends using in situ manipulation of the epoxy matrix reaction type

Polymer ◽

10.1016/j.polymer.2019.05.024 ◽

2019 ◽

Vol 176 ◽

pp. 89-100 ◽

Cited By ~ 3

Author(s):

Hajime Kishi ◽

Kazuyoshi Yamada ◽

Jin Kimura

Keyword(s):

Fracture Toughness ◽

Block Copolymer ◽

Epoxy Matrix ◽

Reaction Type ◽

Copolymer Blends

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Highly diastereo- and enantioselective organocatalytic synthesis of trifluoromethylated erythritols based on the in situ generation of unstable trifluoroacetaldehyde

Organic & Biomolecular Chemistry ◽

10.1039/d0ob02067b ◽

2021 ◽

Author(s):

Kazumasa Funabiki ◽

Toshiya Gotoh ◽

Ryunosuke Kani ◽

Toshiyasu Inuzuka ◽

Yasuhiro Kubota

Keyword(s):

Trifluoromethyl Group ◽

In Situ Generation

A highly diastereo- and enantioselective organocatalytic method to synthesise erythritols bearing a trifluoromethyl group has been investigated.

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Reductive Cleavage of Secondary Sulfonamides: Converting Terminal Functional Groups into Versatile Synthetic Handles

10.26434/chemrxiv.9925145 ◽

2019 ◽

Author(s):

Patrick Fier ◽

Suhong Kim ◽

Kevin M. Maloney

Keyword(s):

Functional Groups ◽

Late Stage ◽

Reductive Cleavage ◽

Bioactive Molecules ◽

General Method

Sulfonamides are pervasive in drugs and agrochemicals, yet are typically considered as terminal functional groups rather than synthetic handles. To enable the general late-stage functionalization of secondary sulfonamides, we have developed a mild and general method to reductively cleave the N-S bonds of sulfonamides to generate sulfinates and amines, components which can further react <i>in-situ</i> to access a variety of other medicinally relevant functional groups. The utility of this platform is highlighted by the selective manipulation of several complex bioactive molecules.

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Recent advances in Minisci-type reactions and applications in organic synthesis

Current Organic Chemistry ◽

10.2174/1385272824999201230211157 ◽

2020 ◽

Vol 24 ◽

Author(s):

Wengui Wang ◽

Shoufeng Wang

Keyword(s):

Free Radical ◽

Hydrogen Atom ◽

Organic Synthesis ◽

Radical Reactivity ◽

Atom Loss ◽

Radical Generation ◽

In Situ Generation ◽

Thermal Cleavage ◽

Synthetic Chemist

Abstract:: Minisci-type reactions have become widely known as reactions that involve the addition of carbon-centered radicals to basic heteroarenes followed by formal hydrogen atom loss. While the originally developed protocols for radical generation remain in active use today, in recent years by a new array of radical generation strategies allow use of a wider variety of radical precursors that often operate under milder and more benign conditions. New transformations based on free radical reactivity are now available to a synthetic chemist looking to utilize a Minisci-type reaction. Radical-generation methods based on photoredox catalysis and electrochemistry, which utilize thermal cleavage or the in situ generation of reactive radical precursors, have become popular approaches. Our review will cover the remarkably literature that has appeared on this topic in recent 5 years, from 2015-01 to 2020-01, in an attempt to provide guidance to the synthetic chemist, on both the challenges that have been overcome and applications in organic synthesis.

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