Direct Catalytic Anti-Markovnikov Addition of Carboxylic Acids to Alkenes

Perkowski, Andrew J.; Nicewicz, David A.

doi:10.1021/ja4057294

Cited by 190 publications

(110 citation statements)

References 17 publications

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“…S15 †) was the key analysis to confirm the thiol addition to the allyl functionality in AA. The result supported an anti Markovnikov reaction 50 which would create diagnostic methylene signals in the same spin system. More specifically, HSQC TOCSY revealed cross peak correlation between the newly formed aliphatic signals at 13 Fig.…”

Section: Thiol-ene Reaction Testsupporting

confidence: 52%

A one-pot biomimetic synthesis of selectively functionalized lignins from monomers: a green functionalization platform

2018

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Lignin is the most abundant renewable source of phenolic compounds with great application potential in renewable materials, biofuels and platform chemicals. The current technology for producing celluloserich fibers co-produces heterogeneous lignin, which includes an untapped source of monomeric phenolics. One such monomer also happens to be the main monomer in soft wood lignin biosynthesis, namely coniferyl alcohol. Herein, we investigate the potential of coniferyl alcohol as a platform monomer for the biomimetic production of tailored functionalized oligolignols with desirable properties for material synthesis. Accordingly, a bifunctional molecule with at least one carboxyl-ended functionality is included with coniferyl alcohol in biomimetic lignin synthesis to, in one pot, produce a functionalized lignin. The functionalization mechanism is a nucleophilic addition reaction to the quinone methide intermediate of lignin polymerization. The solvent system applied was pure water or 50% aqueous acetone. Several bifunctional molecules differing in the second functionality were successfully inserted in the lignin demonstrating the platform component of this work. Detailed characterization was performed by a combination of NMR techniques which include 1 H NMR, COSY-90, 31 P NMR, 13 C NMR, 13 C APT, HSQC, HMBC and HSQC TOCSY. Excellent selectivity towards benzylic carbon and a high functionalization degree were noted. The structure of lignin was tailored through the solvent system choice, with 50% aqueous acetone producing a skeletal structure favorable for a high degree of functionalization. Finally, material concepts are demonstrated using classical thiol-ene-and Diels-Alder-chemistries to show the potential for the thermoset and thermoplastic concepts, respectively. The functionalization concept presents unprecedented opportunities for the green production of lignin-based recyclable biomaterials.

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Section: Thiol-ene Reaction Testsupporting

confidence: 52%

A one-pot biomimetic synthesis of selectively functionalized lignins from monomers: a green functionalization platform

2018

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“…In many cases, thiophenol catalysts proved superior due to the faster rate of HAT between carbon-centered radicals and thiols. As shown in Scheme 14, these transformations include intermolecular hydroacetoxylation, 64 intra- and intermolecular hydroamination, 65 a range of novel polar radical crossover cycloadditions, 66 as well as a method for the direct anti-Markovnikov addition of mineral acids to styrenes. 67 …”

Section: Dual Photoredox Organocatalysis: Hydrogen Atom Transfermentioning

confidence: 99%

Photoredox Catalysis in Organic Chemistry

2016

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In recent years, photoredox catalysis has come to the forefront in organic chemistry as a powerful strategy for the activation of small molecules. In a general sense, these approaches rely on the ability of metal complexes and organic dyes to convert visible light into chemical energy by engaging in single-electron transfer with organic substrates, thereby generating reactive intermediates. In this Perspective, we highlight the unique ability of photoredox catalysis to expedite the development of completely new reaction mechanisms, with particular emphasis placed on multicatalytic strategies that enable the construction of challenging carbon–carbon and carbon–heteroatom bonds.

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“…In this case, no anion is formed owing to the pK a value; indeed, the base-substrate complex decreases the N-H bond-dissociation free energy (BDFE) to a potential reachable for the iridium-based catalyst. Through this new approach, several pyrrolidinones (45)(46)(47), thiazolidinone 48, and oxazolidinone 49 are accessible. As shown in the mechanism in Scheme 10, the PCET step is crucial for the hydroamidation Scheme 11.…”

Section: +mentioning

confidence: 99%

“…[51] On the basis of their previous work concerning hydroacetoxylation (Scheme 29), [45] they introduced catalytic quantities of base to increase the nucleophilicity of the acid function. Thiol derivatives were chosen as HADs and used in catalytic amounts.…”

Section: Multiple-bond-centered Radical-mediated Reactivitymentioning

confidence: 99%