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1.
J Org Chem ; 88(2): 1235-1244, 2023 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-36606370

RESUMO

We report a photoinduced decarbonylative rearrangement of diazabicyclo[2.2.2]octenone in the facile synthesis of a functionalized diazabicyclo[4.1.0]heptene skeleton, a unique derivative of the hydropyridazine type structure which could be found in a variety of biologically active natural products. The scope of functional group compatibility in the photoreaction was examined by taking advantage of the easy access of the heterobicyclo[2.2.2] structure from the Diels-Alder reaction of masked o-benzoquinones. 4-Phenyl-1,2,4-triazoline-3,5-dione served as the dienophile which provided the adjacent N-N unit in hexahydropyridazine-type products of subsequent photorearrangement.

2.
Molecules ; 26(23)2021 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-34885794

RESUMO

A novel synthetic pathway to approach 3-(imino)isoindolin-1-ones by the Co-catalyzed cyclization reaction of 2-bromobenzamides with carbodiimides has been developed. This catalytic reaction can tolerate a variety of substituents and provide corresponding products in moderate yields for most cases. According to the literature, the reaction mechanism is proposed through the formation of a five-membered aza-cobalacycle complex, which carries out the following reaction subsequence, including nucleophilic addition and substitution, to furnish the desired structures.

3.
J Org Chem ; 85(4): 2040-2047, 2020 02 21.
Artigo em Inglês | MEDLINE | ID: mdl-31886669

RESUMO

We report the use of a rhodium(II) dimer in visible light photoredox catalysis for the aerobic oxidation of arylboronic acids to phenols under mild conditions. Spectroscopic and computational studies indicate that the catalyst Rh2(bpy)2(OAc)4 (1) undergoes metal-metal to ligand charge transfer upon visible light irradiation, which is responsible for catalytic activity. Further reactivity studies demonstrate that 1 is a general photoredox catalyst for diverse oxidation reactions.

4.
J Org Chem ; 84(16): 10172-10182, 2019 08 16.
Artigo em Inglês | MEDLINE | ID: mdl-31298030

RESUMO

We report the formal synthesis of (±)-pentalenolactone A methyl ester from simple 2-methoxyphenol. The key features of our route are as follows: a Diels-Alder reaction of masked o-benzoquinone to assemble the functionalized bicyclo[2.2.2]octenone, a continuous-flow oxa-di-π-methane rearrangement for building the diquinane core (AB ring), and an oxidative cleavage/oxidation sequence for annulation of the δ-lactone (C ring).

5.
J Org Chem ; 82(21): 11626-11630, 2017 11 03.
Artigo em Inglês | MEDLINE | ID: mdl-28980464

RESUMO

Herein we report an effective and simple preparation method of substituted azoxybenzenes by reductive dimerization of nitrosobenzenes. This procedure requires no additional catalyst/reagent and can be applied to substrates with a wide range of substitution patterns.

6.
J Org Chem ; 80(21): 10979-91, 2015 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-26473385

RESUMO

The marasmane sesquiterpenoid structure can be found in the skeleton of a variety of natural products bearing interesting bioactivity. The unique fused-5,6,3-tricyclic ring structure, in which the rings are cis-fused and the five- and three-membered rings are mutually trans, provides a synthetic challenge for organic chemists. In this work, we took advantage of the photoinduced decarbonylative rearrangement of bicyclo[2.2.2]octenone to develop a new methodology for construction of the highly functionalized fused-5,6,3-tricyclic ring structure in a concise reaction sequence.


Assuntos
Compostos Bicíclicos com Pontes/química , Ciclo-Octanos/síntese química , Sesquiterpenos/síntese química , Fenômenos Bioquímicos , Ciclo-Octanos/química , Estrutura Molecular , Sesquiterpenos Policíclicos , Sesquiterpenos/química
7.
Chemistry ; 20(18): 5240-3, 2014 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-24668584

RESUMO

The first Co/Pd-cocatalyzed intramolecular C-H amination and aziridination reactions were developed. Sulfamate esters were converted to oxathiazinanes by using CoPd(OAc)4 as catalyst and PhI(OAc)2 as oxidant. The mutual presence of both Co and Pd is crucial for the catalytic activity. This combination of two metals with simple acetate ligands provides an economical alternative to the Rh-catalyzed insertion of nitrenoids into C-H bonds.


Assuntos
Ácido Acético/química , Aziridinas/química , Cobalto/química , Complexos de Coordenação/química , Paládio/química , Aminação , Catálise , Ésteres/química , Ligantes , Oxidantes/química , Ácidos Sulfônicos/química , Tiazinas/química
8.
J Am Chem Soc ; 133(6): 1760-2, 2011 Feb 16.
Artigo em Inglês | MEDLINE | ID: mdl-21247109

RESUMO

A chemo- and regioselective α-hydroxylation reaction of carbonyl compounds with molecular oxygen as oxidant is reported. The hydroxylation reaction is catalyzed by a dinuclear Pd(II) complex, which functions as an oxygen transfer catalyst, reminiscent of an oxygenase. The development of this oxidation reaction was inspired by discovery and mechanism evaluation of previously unknown Pd(III)-Pd(III) complexes.


Assuntos
Cetonas/química , Oxigênio/química , Paládio/química , Catálise , Hidroxilação
9.
ACS Omega ; 5(1): 918-925, 2020 Jan 14.
Artigo em Inglês | MEDLINE | ID: mdl-31956846

RESUMO

A useful oxidation of C-H bond of benzylic acetals has been achieved. This method avoids the use of stoichiometric metals and is compatible with the presence of both electron-donating and electron-withdrawing substituents on the aromatic ring. Oxidation was carried out by rapid microwave irradiation of benzylic acetals with PhI(OAc)2 as the oxidant. This led to the oxidation of acetals into 2-acetoxy-1,3-dioxolanes. Furthermore, this transformation protocol encompasses a wide range of valuable conversions of these useful synthons into different carboxylic acid derivatives.

10.
J Org Chem ; 74(4): 1632-9, 2009 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-19199660

RESUMO

Inverse-electron-demand Diels-Alder reactions of masked o-benzoquinones 2 with phenyl vinyl sulfide and phenyl vinyl selenide furnished highly functionalized bicyclo[2.2.2]octenone derivatives 3 and 4, respectively, in excellent regio- and stereoselectivities and yields up to 90%. The bicyclo[2.2.2]octenone derivatives 3 with the sulfur functionality were subjected to an oxidation-elimination process to furnish bicyclo[2.2.2]octadienone systems 7 in good yields. During the reduction process, the Diels-Alder adducts 3e and 4e led to 8, whereas the carbon-centered radicals generated from the other adducts 3a-d and 4a-d provided various rearranged products 9-13 depending on the substitution pattern and reagents utilized (Raney-Ni or n-Bu(3)SnH). Surprisingly these radicals showed preference for the carbonyl functionality to the olefinic double bond, leading to interesting rearrangement reactions of mechanistic importance and possible synthetic utility. Interestingly the alcohols obtained from the reduction of Diels-Alder adducts 3a-d underwent desulfurization smoothly to give desulfurized products in high yields; thus a detoured method of "reduction-desulfurization-oxidation" provides an entry to desulfurized bicyclo[2.2.2]octenones without rearrangement.

12.
Chem Asian J ; 3(8-9): 1422-9, 2008 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-18663719

RESUMO

The synthesis of a series of bicyclo[4.2.2]octenones and bicyclo[3.2.2]heptenones by 1,3- or 1,2-migration reaction from 2-vinylbicyclo[2.2.2]octenols is reported. These ring-expansion reactions were accomplished under basic or neutral conditions. Whether 1,3- or 1,2-migration takes place depends on endo- or exocyclic olefin displacement in the substrates.


Assuntos
Compostos Bicíclicos com Pontes/síntese química , Carbono/química , Furanos/química , Octanos/química , Compostos de Vinila/síntese química , Alcenos/química , Ânions/química , Compostos Bicíclicos com Pontes/química , Modelos Moleculares , Estrutura Molecular , Compostos de Vinila/química
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