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1.
Dalton Trans ; 53(26): 10829-10833, 2024 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-38898710

RESUMO

The first anionic pentacoordinated group 14 compounds bearing a phenylethynyl substituent were successfully synthesized and crystallographically characterized. The synthesized ate-type compounds were stable in air, water, and some acids, allowing their application as reagents for the nucleophilic alkynylation of carbon electrophiles.

2.
Chem Sci ; 14(3): 485-490, 2023 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-36741523

RESUMO

Amine catalysts have emerged as an invaluable tool in organic synthesis. Iminium, enamine, and enamine radical cation species are representative activation modes of amine catalysis. However, the development of new amine catalysis activation modes that enable novel synthetic strategies remains highly desirable. Herein, we report streptocyanine as a new amine catalysis activation mode, which enables the skeletal editing of pyridine rings to benzene rings. N-Arylation of pyridines bearing an alkenyl substituent at the 3-position generates the corresponding N-arylpyridiniums. The resulting pyridinum reacts with a catalytic amount of piperidine to afford a streptocyanine intermediate. Catalytically generated streptocyanine forms a benzene ring via a ring-closing reaction, thereby releasing the amine catalyst. Consequently, the alkene moiety in the starting pyridines is incorporated into the benzene ring of the products. Pyridiniums bearing various alkene moieties were efficiently converted to formyl-substituted benzene derivatives. Mechanistic studies support the postulation that the present catalytic process was intermediated by streptocyanine. In this reaction system, streptocyanine could be regarded as a new activation mode of amine catalysis.

3.
Org Biomol Chem ; 20(48): 9600-9603, 2022 12 14.
Artigo em Inglês | MEDLINE | ID: mdl-36412506

RESUMO

In this study, we propose that the trifluoromethylated thermally activated delayed fluorescent molecule 4[Cz(CF3)2]IPN is a versatile organic photocatalyst that can be used for electron-transfer-driven reactions requiring a photocatalyst with high oxidizing power and energy-transfer-driven reactions that require an Ir photocatalyst. 4[Cz(CF3)2]IPN was used in radical reactions via electron transfer and dearomative cycloaddition reactions via energy transfer.


Assuntos
Corantes , Elétrons , Fluorescência , Transporte de Elétrons , Transferência de Energia
4.
J Org Chem ; 87(11): 7565-7573, 2022 06 03.
Artigo em Inglês | MEDLINE | ID: mdl-35578794

RESUMO

Herein, we report the transition-metal-free O-arylation of alcohols and phenols with S-arylphenothiaziniums, which can be easily synthesized from boronic acids. Aryl substituents derived from arylboronic acids were selectively introduced into the hydroxy groups in alcohols and phenols, and a variety of aryl ethers were synthesized. This selectivity is supported by theoretical calculations.


Assuntos
Álcoois , Elementos de Transição , Catálise , Cobre , Éteres , Fenóis
5.
Org Lett ; 23(24): 9664-9668, 2021 Dec 17.
Artigo em Inglês | MEDLINE | ID: mdl-34878797

RESUMO

Herein, we report the development of a transition-metal-free oxidative C(sp2)-C(sp2) coupling of readily available boronic acids and organolithiums via phenothiazinium ions. Various biaryl, styrene, and diene derivatives were obtained using this reaction system. The key to this process is N-methylphenothiazine S-oxide (PTZSO), which allows efficient conversion of boronic acids to phenothiazinium ions. The mechanism of phenothiazinium formation using PTZSO was investigated using theoretical calculations and experiments, which provided insight into the unique reactivity of PTZSO.

6.
Dalton Trans ; 50(44): 16003-16012, 2021 Nov 16.
Artigo em Inglês | MEDLINE | ID: mdl-34734937

RESUMO

The first phosphinoboronic ester bearing a fused bicyclic framework was synthesised by either deprotonation and hydride abstraction or Rh-catalysed dehydrogenation of a hydrophosphineboronic ester. The phosphinoboronic ester reacted as a Lewis acid with KF/18-crown-6, pyridine and DMAP to give the corresponding adducts. Furthermore, its crystal structure shows a remarkably short P-B bond in comparison with other P-B bonded derivatives in spite of the trigonal pyramidal geometry of the phosphorus. Consistent with the phosphorus pyramidality, the π-type donor-acceptor interaction of the P-B bond is small as revealed by the DFT calculations. The P-B bond shared within the fused six-membered rings has to shorten because of the geometrical requirement and high s-character of the boron.

7.
Org Lett ; 23(16): 6257-6261, 2021 08 20.
Artigo em Inglês | MEDLINE | ID: mdl-34324819

RESUMO

The intermolecular dearomative cycloaddition of acidified bicyclic azaarenes with olefins was recently reported. We report here the crucial role of the acid in the dearomative photocycloaddition of quinolines to olefins. Experimental and theoretical results show that the key role of the protonation of quinolines is not to promote the energy transfer but to enhance the reactivity of the triplet state of quinolines toward olefins.

8.
Org Lett ; 23(15): 6126-6130, 2021 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-34314185

RESUMO

Herein we report a method for converting para-substituted pyridine rings into meta-dialkylamino-substituted benzene rings through sequential ring-opening and ring-closing reactions. The nitrogen atom in the pyridine rings was replaced with a methine group, and a dialkylamino substituent was introduced onto the original unsubstituted carbon atom in the pyridine rings. This process can be formally regarded as a hybrid of the skeletal editing and C-H amination of pyridine rings.

9.
Chemistry ; 27(22): 6713-6718, 2021 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-33382504

RESUMO

Herein, a photocatalytic Giese-type reaction with alkylsilicates bearing C,O-bidentate ligands as stable alkyl radical precursors has been reported. The alkylsilicates were prepared in one step from organometallic reagents. Not only primary, secondary, and tertiary alkyl radicals, but also elusive methyl radicals, could be generated by using the present reaction system. The generated radicals were trapped by electron-deficient olefins bearing various functional groups to give the desired alkyl adducts. The silicon byproduct can be recovered after the photoreaction. The radical generation process was investigated by theoretical calculations, which provided an insight into the facile generation of methyl radicals from methylsilicate bearing C,O-bidentate ligands.

10.
Chem Commun (Camb) ; 56(90): 13995-13998, 2020 Nov 12.
Artigo em Inglês | MEDLINE | ID: mdl-33094752

RESUMO

Aryllithiums are one of the most common and important aryl nucleophiles; nevertheless, methods for arylation of aryllithums to produce biaryls have been limited. Herein, we report arylation of aryllithiums with S-arylphenothiazinium ions through selective ligand coupling of intermediary sulfuranes. Various unsymmetrical biaryls could be obtained without transition-metal catalysis.

11.
Chem Commun (Camb) ; 56(69): 10006-10009, 2020 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-32725001

RESUMO

We report the photocatalytic C-H alkylations of heteroarenes with alkylsilicates bearing C,O-bidentate ligands under acidic conditions. Irradiation of heteroaromatics in the presence of the silicates and trifluoroacetic acid produced the corresponding alkylated compounds. The present reaction system does not require any terminal oxidant although the reaction seems to be a formal oxidation reaction. This study demonstrates that alkylsilicates can be used in photocatalytic radical chemistry under acidic conditions.

12.
J Am Chem Soc ; 142(32): 13886-13897, 2020 08 12.
Artigo em Inglês | MEDLINE | ID: mdl-32664727

RESUMO

Enzymes involved in the biosynthesis of ribosomally synthesized and post-translationally modified peptides (RiPPs) often have relaxed specificity profiles and are able to modify diverse substrates. When several such enzymes act together during precursor peptide maturation, a multitude of products can form, yet usually the biosynthesis converges on a single natural product. For the most part, the mechanisms controlling the integrity of RiPP assembly remain elusive. Here, we investigate the biosynthesis of lactazole A, a model thiopeptide produced by five promiscuous enzymes from a ribosomal precursor peptide. Using our in vitro thiopeptide production (FIT-Laz) system, we determine the order of biosynthetic events at the individual modification level and supplement this study with substrate scope analysis for participating enzymes. Our results reveal an unusual but well-defined assembly process where cyclodehydration, dehydroalanine formation, and azoline dehydrogenation events are intertwined due to minimal substrate recognition requirements characteristic of every lactazole enzyme. Additionally, each enzyme plays a role in directing LazBF-mediated dehydroalanine formation, which emerges as the central theme of the assembly process. Cyclodehydratase LazDE discriminates a single serine residue for azoline formation, leaving the remaining five as potential dehydratase substrates. Pyridine synthase LazC exerts kinetic control over LazBF to prevent the formation of overdehydrated thiopeptides, whereas the coupling of dehydrogenation to dehydroalanine installation impedes generation of underdehydrated products. Altogether, our results indicate that substrate-level cooperation between the biosynthetic enzymes maintains the integrity of lactazole assembly. This work advances our understanding of RiPP biosynthesis processes and facilitates thiopeptide bioengineering.


Assuntos
Hidroliases/metabolismo , Óxido Nítrico Sintase/metabolismo , Estrutura Molecular , Streptomyces/química
13.
Org Lett ; 22(7): 2822-2827, 2020 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-32207629

RESUMO

We report the photocatalytic C-H amination of aromatics overcoming redox potential limitations. Radical cations of aromatic compounds are generated photocatalytically using Ru(phen)3(PF6)2, which has a reduction potential at a high oxidation state (Ered(RuIII/RuII) = +1.37 V vs SCE) lower than the oxidation potentials of aromatic substrates (Eox = +1.65 to +2.27 V vs SCE). The radical cations are trapped with pyridine to give N-arylpyridinium ions, which were converted to aromatic amines.

14.
Chem Commun (Camb) ; 55(59): 8575-8578, 2019 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-31274134

RESUMO

A benzene ring was formed to connect a carbonyl group of various methyl ketones with a π-conjugated group through a p-phenylene linker. Methyl ketones and streptocyanines were used as the C1 and C5 sources, respectively, in the (5+1) annulation, which could form donor-π-acceptor molecules.

15.
Angew Chem Int Ed Engl ; 56(21): 5882-5885, 2017 05 15.
Artigo em Inglês | MEDLINE | ID: mdl-28436088

RESUMO

The first trihydroborate bearing a pentacoordinated phosphorus atom was synthesized as a new P-B bonded compound. Hydride abstraction of the trihydroborate gave an intermediary dihydroborane, which showed hydroboration reactivity and was trapped with pyridine whilst maintaining the P-B bond. The dihydroborane underwent a rearrangement, which involved a double ring expansion to compensate for the unbalanced coordination states of the phosphorus and boron atoms, to give a new fused bicyclic phosphine-boronate.

16.
Dalton Trans ; 45(48): 19374-19379, 2016 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-27878159

RESUMO

The first dianionic compound bearing a bond between two pentacoordinated tin atoms, a distannate, was synthesized in a stable form by using two sets of an electron-withdrawing C,O-bidentate ligand on each tin atom. The structure of the distannate was determined by NMR spectroscopy and X-ray crystallographic analysis. The Sn-Sn bond of the distannate was shown to be a single bond featuring high s-character. The 1J(Sn-Sn) coupling constant was larger than that of Sn(sp3)-Sn(sp3) bonds found in most hexaorganodistannanes. This bond feature was also supported by computational studies. The Sn-Sn bond was cleaved by treatment with hydrochloric acid, which shows a different reactivity to the homonuclear bonds of pentacoordinated disilicates and digermanates.

17.
Dalton Trans ; 44(37): 16256-65, 2015 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-26205678

RESUMO

(E)-4,4'-Dimethyl-2,2'-disilylazobenzenes were synthesized. Double intramolecular N∙∙∙Si coordination in the bis(fluorodimethylsilyl) and bis(trifluorosilyl) derivatives was confirmed using X-ray crystallographic analysis and (29)Si NMR spectroscopy. In the absorption bands, due to the π,π* transitions, introduction of silyl groups was found to cause a bathochromic shift. In contrast to most azobenzenes, which do not fluoresce at all, the (E)-2,2'-bis(trifluorosilyl)azobenzene derivative with the N∙∙∙Si coordination fluoresced a yellow-green colour at room temperature. Methyl and trifluorosilyl groups lowered the n and π* orbitals, as revealed by DFT calculations. As a result, the lowest singlet excitation energy state is found to be the allowed π,π* transition, different from the forbidden n,π* transition in general azobenzenes, as revealed by TD-DFT calculations. The allowed transition character of the lowest singlet excited state and moderately rigid conformation of the azo moiety, provided by the double N∙∙∙Si coordination, account for the fluorescence emission. Nevertheless, the N∙∙∙Si coordination is weak enough to be cleaved upon photoexcitation, and thus the (E)-2,2'-disilylazobenzenes undergo photoisomerization to the (Z)-isomers. Both the photoisomerization and fluorescence emission properties of the azobenzene moiety have been achieved for the first time. After photoisomerization of the (E)-2,2'-disilylazobenzenes to the corresponding (Z)-isomer, they do not fluoresce. This change in the fluorescence intensity upon photoisomerization is useful for the regulation of fluorescence properties. Therefore, this compound can be recognized as a unique photoisomerizable fluorophore to regulate the fluorescence intensity using a single light source.

18.
Dalton Trans ; 42(45): 15826-34, 2013 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-24013924

RESUMO

Azobenzenes are constituents of the commonly and widely used azo dyes. Many dyes, except for the azo dyes, have been utilized for fluorescent materials. However, there are only a few fluorescent azobenzene derivatives and their fluorescence efficiencies are quite low. The current perspective provides an account of the fluorescent azobenzenes and aromatic aldimines featuring an N-B interaction. Incorporation of the intramolecular N-B interaction by using the bis(pentafluorophenyl)boryl group makes the azobenzenes and aromatic aldimines fluorescent with a range of colours. Some of them fluoresce with extraordinarily high fluorescence quantum yields. Their synthesis, structures, fluorescence properties, and applications are discussed.

19.
Chem Commun (Camb) ; 49(88): 10373-5, 2013 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-23807626

RESUMO

Organosilanes bearing a phosphine imide moiety were synthesized and crystallographically characterized. Reaction of the pentacoordinated hydrodiphenylsilyl derivative with water gave [2-(diphenylphosphino)phenyl]diphenylsilanol accompanied by both reduction of the phosphine imide moiety and hydrolytic oxidation of the Si-H moiety.

20.
Dalton Trans ; 41(37): 11491-6, 2012 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-22893026

RESUMO

Control of coordination modes of a ligand in metal complexes is significant because the coordination modes influence catalytic properties of transition metal catalysts. Reactions of 2-diphenylphosphinoazobenzenes, which are in equilibrium with the inner phosphonium salts, with ZnCl(2), W(CO)(5)(THF), and PtCl(2)(cod) gave three different coordination types of metal complexes with distinctive UV-vis absorptions. All the complexes were characterized by X-ray crystallographic analyses. In the zinc and tungsten complexes, the source molecule functions as an amide ligand and a phosphine ligand, respectively. In the platinum complex, the phosphorus molecule works as a tridentate ligand with formation of a carbon-platinum bond.

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