Bioinspired Synthesis of a Sedaxane Metabolite Using Catalytic Vanadyl Acetylacetonate and Molecular Oxygen

Tyagi, Sameer; Cook, Christopher David; DiDonato, Dana; Key, Jeffrey A.; McKillican, Bruce P.; Eberle, William J.; Carlin, T. J.; Hunt, David A.; Marshall, Samantha J.; Bow, Nichola L.

doi:10.1021/acs.joc.5b01700

Cited by 17 publications

(11 citation statements)

References 39 publications

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“…Tyagi and co-workers exploited the protected product of coupling benzophenone imine in their bioinspired synthesis of 449 , a metabolite of the fungicide sedaxane ( Scheme 112 a). 386 L6 was a suitable supporting ligand for the reaction between chiral aryl bromide 446 and benzophenone imine, furnishing intermediate 447 in 67% yield. Prior to cleavage of the imine, a Kulinkovich cyclopropanation was carried out, and subsequent in situ acidic deprotection gave rise to the target primary aniline 448 in 54% yield.…”

Section: Ammonia Equivalents and Ammoniamentioning

confidence: 99%

Applications of Palladium-Catalyzed C–N Cross-Coupling Reactions

2016

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Pd-catalyzed cross-coupling reactions that form C–N bonds have become useful methods to synthesize anilines and aniline derivatives, an important class of compounds throughout chemical research. A key factor in the widespread adoption of these methods has been the continued development of reliable and versatile catalysts that function under operationally simple, user-friendly conditions. This review provides an overview of Pd-catalyzed N-arylation reactions found in both basic and applied chemical research from 2008 to the present. Selected examples of C–N cross-coupling reactions between nine classes of nitrogen-based coupling partners and (pseudo)aryl halides are described for the synthesis of heterocycles, medicinally relevant compounds, natural products, organic materials, and catalysts.

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Section: Ammonia Equivalents and Ammoniamentioning

confidence: 99%

Applications of Palladium-Catalyzed C–N Cross-Coupling Reactions

2016

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“…This reactivity will be discussed in more detail in Section 3. Lin, Yao, and co-workers found that alkynes (191) can be used for the Pd-catalyzed β-functionalization of cyclopropyl alcohols (190), forming β-alkenylketones (192) (Scheme 47). 115 The proposed catalytic cycle is shown in Scheme 47.…”

Section: β-Functionalization With Heteroatom−x Electrophilesmentioning

confidence: 99%

Selective Carbon–Carbon Bond Cleavage of Cyclopropanols

et al. 2020

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The carbon–carbon (C–C) bond cleavage of cyclopropanols is a wide area of research with much current activity. This review highlights new developments in this area over the past two decades. A summary is made of the three main reactivity modes, namely, homoenolate chemistry, β-keto radical chemistry, and acid-catalyzed ring-opening, as well as all other methods for the C–C bond cleavage and functionalization of cyclopropanols, including base-mediated ring-opening, metal-catalyzed C–C insertions and eliminations, oxidative fragmentation using hypervalent iodine reagents, reactions of donor–acceptor cyclopropanols, and pericylic reactions. Emphasis is placed on the synthetic utility of cyclopropanols and related derivatives, which have emerged as unique three-carbon synthons.

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“…For the synthesis of the key intermediate of sedaxane 109 , the aniline 107 , several synthetic routes have been reported in process patents. , The most favorable (large-scale) methodology is the Pd-catalyzed benzylamination (PhCH 2 NH 2 ) of the chlorobenzene precursor 105 in the presence of an appropriate carbene ligand 106 (Figure ). ,, After catalytic cleavage (using Pd/C, H 2 ) of the protecting group, o -biscyclopropyl aniline 107 was obtained in excellent yield (>85% yield over two steps). Finally, the aniline 107 was treated with the appropriate acyl chloride 108 in the presence of a cheap base such as triethylamine to give sedaxane 109 in very good yield.…”

Section: Carbon–nitrogen Bond Forming Cross-couplingsmentioning

confidence: 99%

Palladium-Catalyzed Cross-Coupling Reactions: A Powerful Tool for the Synthesis of Agrochemicals

Devendar

Kang

et al. 2018

J. Agric. Food Chem.

309

165

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Pd-catalyzed cross-coupling reactions have become essential tools for the construction of carbon-carbon and carbon-heteroatom bonds. Over the last three decades, great efforts have been made with cross-coupling chemistry in the discovery, development, and commercialization of innovative new pharmaceuticals and agrochemicals (mainly herbicides, fungicides, and insecticides). In view of the growing interest in both modern crop protection and cross-coupling chemistry, this review gives a comprehensive overview of the successful applications of various Pd-catalyzed cross-coupling methodologies, which have been implemented as key steps in the synthesis of agrochemicals (on R&D and pilot-plant scales) such as the Heck, Suzuki, Sonogashira, Stille, and Negishi reactions, as well as decarboxylative, carbonylative, α-arylative, and carbon-nitrogen bond bond-forming cross-coupling reactions. Some perspectives and challenges for these catalytic coupling processes in the discovery of agrochemicals are briefly discussed in the final section. The examples chosen demonstrate that cross-coupling chemistry approaches open-up new, low-cost, and more efficient industrial routes to existing agrochemicals, and such methods also have the capability to lead the new generation of pesticides with novel modes of action for sustainable crop protection.

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Bioinspired Synthesis of a Sedaxane Metabolite Using Catalytic Vanadyl Acetylacetonate and Molecular Oxygen

Cited by 17 publications

References 39 publications

Applications of Palladium-Catalyzed C–N Cross-Coupling Reactions

Applications of Palladium-Catalyzed C–N Cross-Coupling Reactions

Selective Carbon–Carbon Bond Cleavage of Cyclopropanols

Palladium-Catalyzed Cross-Coupling Reactions: A Powerful Tool for the Synthesis of Agrochemicals

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