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1.
Org Biomol Chem ; 21(37): 7567-7571, 2023 Sep 27.
Artigo em Inglês | MEDLINE | ID: mdl-37671616

RESUMO

An efficient stereo-controlled synthesis of enyne and enediyne derivatives, via sequential Suzuki-Miyaura coupling reactions from easily prepared 1-alkene-1,2-diboronic esters and alkynyl bromides, is reported. The resulting enyne boronic esters were subjected to Borono-Mannich and Suzuki coupling reactions independently to obtain α,ß-unsaturated aminoester and tri-substituted olefin derivatives, respectively. Additionally, divergent syntheses of triazole and cyclopropylboronate derivatives are also reported.

2.
J Org Chem ; 88(9): 5772-5779, 2023 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-37058287

RESUMO

A facile double oxidative annulation of (en-3-yn-1-yl)phenylbenzamides was developed allowing us to synthetize fused tetracyclic compounds. Under copper catalysis, the reaction proceeds with high efficiency and leads to new indolo[1,2-a]quinolines via a decarbonylative double oxidative annulation. On the other hand, under ruthenium catalysis, new isoquinolin-1[2H]-ones were obtained via a double oxidative annulation.

3.
Chirality ; 35(4): 227-246, 2023 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-36735567

RESUMO

2-Amino[2.2]paracyclophane reacts with salicylaldehyde or 2-hydroxyacetophenone to yield imines that then give access to a new series of boranils (8b-d) upon complexation with BF2 . These novel boron-containing compounds display both planar and axial chiralities and were examined experimentally and computationally. In particular, their photophysical and chiroptical properties were studied and compared to newly prepared, simpler boranils (9a-d) exhibiting axial chirality only. Less sophisticated chiral architectures were shown to demonstrate overall stronger circularly polarized luminescence (CPL) activity.

4.
Dalton Trans ; 51(32): 12161-12169, 2022 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-35876615

RESUMO

The preparation and characterization of three new complexes, namely [Pt(1,3-bis(4-triphenylamine-pyridin-2-yl)-4,6-difluoro-benzene)Cl] ([PtL1Cl]), [Pt(1,3-bis(4-triphenylamine-pyridin-2-yl)-5-triphenylamine-benzene)Cl] ([PtL2Cl]), and [Pt(1,3-bis(4-triphenylamine-pyridin-2-yl)-5-mesityl-benzene)Cl] ([PtL3Cl]), is reported. All of them are highly luminescent in dilute deaerated dichloromethane solution (Φlum = 0.88-0.90, in the yellow-green region; the λmax,em in nm for the monomers are: 562, 561 and 549 for [PtL1Cl], [PtL2Cl] and [PtL3Cl], respectively).[PtL1Cl] is the most appealing, being characterized by a very long lifetime (103.9 µs) and displaying intense NIR emission in concentrated deaerated solution (Φlum = 0.66) with essentially no "contamination" by visible light < 600 nm. This complex allows the fabrication of both yellow-green and deep red/NIR OLEDs; OLED emissions are in the yellow-green (CIE = 0.38, 0.56) and deep red/NIR (CIE = 0.65, 0,34) regions, for [PtL1Cl] 8 wt% (with 11% ph/e EQE) and pure [PtL1Cl] (with 4.3% ph/e EQE), respectively.

5.
J Org Chem ; 87(12): 7649-7657, 2022 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-35638869

RESUMO

A Simmons-Smith stereodefined procedure for the synthesis of cyclopropyl-1,2-bis(boronates) has been developed starting from the corresponding alkenes. The resulting compounds were then subjected to regioselective Suzuki-Miyaura couplings to produce diversely tri- or tetra-substituted arylcyclopropanes in good yields. Further functionalization with 2-lithiothiophene provided 1,2-bis(aryl)cyclopropanes.

6.
Chemistry ; 27(29): 7959-7967, 2021 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-33769616

RESUMO

Mono- and di-boranil-substituted helicenes were prepared by BF2 -borylation of the corresponding anils, readily synthesized by condensation of 2-amino- and 2,15-diamino-helicenes with 4-(diethylamino)salicylaldehyde. After enantiomeric resolution using HPLC, their chiroptical properties including circularly polarized fluorescence in solution and in PMMA films were investigated and rationalized with the help of NMR, X-ray and quantum-chemical calculations.

7.
J Org Chem ; 85(23): 15104-15115, 2020 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-33151061

RESUMO

A stereoselective and convenient route has been demonstrated to access (Z)-1,2-diazido alkenes from the corresponding 1,2-diboronic esters via a copper-mediated reaction with sodium azide. Alternately, mono-functionalization was regioselectively carried out with trimethylsilyl azide as an azidation reactant. The in situ conversion of bis-azides to the corresponding bis-triazoles can be readily achieved in the presence of copper sulfate and sodium ascorbate, while the modification of the catalytic system opened a new convenient route to bis-triazolo-pyrazines, a new class of fused heterocycles.

8.
J Org Chem ; 85(8): 5173-5182, 2020 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-32192328

RESUMO

Complimentary to classical hydroboration and boron-Wittig reactions, a new, efficient access to cyclic 1,3-dienyl boronic esters has been developed via diene or triene metathesis. Subsequently, fused pyrroles were synthesized with a broad substrate scope from the reaction of cyclic 1,3-dienyl boronic esters with arylnitroso compounds using a one-pot hetero-Diels-Alder/ring contraction sequence.

9.
Org Biomol Chem ; 17(23): 5789-5800, 2019 06 12.
Artigo em Inglês | MEDLINE | ID: mdl-31135020

RESUMO

4-Methylenechromanes were prepared via a three-step process from 2-borylated α-methylstyrenes. This sequence is based on a key glyoxylate-ene reaction catalyzed by scandium(iii) triflate. The resulting γ-hydroxy boronates, which cyclise to seven-membered homologues of benzoxaborole on silica gel, were cleanly oxidized with sodium perborate, and then cyclised under Mitsunobu conditions. Additionally, several further functional transformations of 4-methylenechromanes or their precursors were carried out to illustrate the synthetic potential of these intermediates.

10.
Org Lett ; 21(9): 2988-2992, 2019 05 03.
Artigo em Inglês | MEDLINE | ID: mdl-30859834

RESUMO

A convergent and rapid synthesis of original C2,C3-unsaturated, C11,C13-keto-enol macrocycles with a peloruside A skeleton has been developed. These original unsaturated macrocycles constitute valuable platforms to access peloruside A analogues with high diversity. The four-fragment strategy implemented features two aldol-type couplings with the central C12-C14 building block TES-diazoacetone and a late-stage ring-closing metathesis. Enantiopure analogue 18ab showed antiproliferative activity in the low micromolar range on NCI and MCF7 tumor cell lines.

11.
Beilstein J Org Chem ; 14: 2949-2955, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-30546479

RESUMO

In this paper, a new access to several chiral 3-aminoglycals as potential precursors for glycosylated natural products is reported from a common starting material, (-)-methyl-L-lactate. The stereodivergent strategy is based on the implementation of a ring-closing metathesis of vinyl ethers as key step of reaction sequences developed.

12.
J Org Chem ; 83(24): 14861-14881, 2018 12 21.
Artigo em Inglês | MEDLINE | ID: mdl-30457341

RESUMO

An unexpected 1,3-dioxa-[3,3]-sigmatropic rearrangement during the treatment of aryl- and alkenyl-substituted allylic alcohols with activated isocyanates is reported. The reorganization of bonds is highly dependent on the electron density of the aromatic ring and the nature of isocyanate used. This metal-free tandem reaction from branched allyl alcohols initiated by a carbamoylation reaction and followed by a sigmatropic rearrangement thus offers a new access to ( E)-cinnamyl and conjugated ( E, E)-diene carbamates, such as N-acyl and N-sulfonyl derivatives. A computational study was conducted in order to rationalize this phenomenon, and a rearrangement progress kinetic analysis was performed.

13.
J Org Chem ; 83(1): 484-490, 2018 01 05.
Artigo em Inglês | MEDLINE | ID: mdl-29224347

RESUMO

Enantiopure carbo[6]helicenyl boronates were synthesized using a photocyclization reaction as the key step. These compounds were further converted to various amino derivatives using copper-catalyzed azidation or amination and reductive alkylation of benzylazide by a helicenyl dichloroborane. Asymmetric Petasis condensation with glyoxylic acid and morpholine controlled by the helical chirality afforded the corresponding amino esters.

14.
J Org Chem ; 83(2): 843-853, 2018 01 19.
Artigo em Inglês | MEDLINE | ID: mdl-29251507

RESUMO

An efficient and straightforward synthesis of isoquinolines is reported from internal alkenyl boronic esters, easily prepared from the corresponding 1,2-bis(boronates), via a sequential copper-catalyzed azidation/aza-Wittig condensation. This synthetic method has been used to synthesize quinisocaine, a topical anesthetic used for the treatment of pain and pruritus, and further extended to thieno[2,3-c]pyridines by using 2-thiophenecarboxaldehyde as coupling partner in the first step.

15.
J Org Chem ; 82(3): 1803-1811, 2017 02 03.
Artigo em Inglês | MEDLINE | ID: mdl-28056174

RESUMO

An efficient and straightforward synthesis of 1-amino-1H-indenes is reported from 1,2-bis(boronates) via a sequential Suzuki-Miyaura coupling/Petasis cyclization reaction. Starting from the same monoboronic ester intermediates, an intermolecular version of this approach also afforded (Z)-α,ß-unsaturated amino esters in moderate to good yields.

16.
J Org Chem ; 81(11): 4633-44, 2016 06 03.
Artigo em Inglês | MEDLINE | ID: mdl-27163288

RESUMO

An efficient asymmetric synthesis of α-amino allylsilane derivatives is reported. The strategy is based on a [3,3]-allyl cyanate sigmatropic rearrangement from enantioenriched γ-hydroxy alkenylsilyl compounds. The isocyanate intermediate can be trapped by several nucleophiles, opening the way for the preparation of unknown chiral functionalized compounds such as the α-ureido allylsilanes as well as carbamate derivatives. A computational study was conducted to rationalize the complete 1,3-chirality transfer of this kind of rearrangement. Moreover, starting from products bearing a phenyldimethyl silyl substituent, the α-amino silane derivatives or the corresponding disiloxanes can be obtained under hydrogenation conditions in an exclusive way according to the used catalyst.

17.
Angew Chem Int Ed Engl ; 55(3): 1025-9, 2016 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-26636973

RESUMO

The combination of in situ generated α-isocyanato allylboronic esters and aldehydes afforded seven-membered-ring enecarbamates with high levels of diastereo- and enantiocontrol. They were easily converted into diversely substituted 1,3-oxazepan-2-ones. An unprecedented rearrangement of 5-acetoxy-7-aryl or styryl derivatives led to tetrasubstituted pyrrolidines. A computational study provides evidence on the feasibility of the proposed mechanism of this unusual ring contraction.

18.
J Org Chem ; 80(13): 6574-83, 2015 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-26039269

RESUMO

A study of the reactivity of 1-borodienes with nitrosoarene compounds has been carried out showing an outcome that differs according to the hybridization state of the boron moiety. Using an sp(2) boron substituent, a one-pot hetero-Diels-Alder/ring contraction cascade occurred to afford N-arylpyrroles with low to good yields depending on the electronic properties of the substituents on the borodiene, whereas an sp(3) boron substituent led to the formation of stable boro-oxazines with high regioselectivity in most of the cases, in moderate to good yields. (1)H and (11)B NMR studies on two boro-oxazine regioisomers showed that selective deprotection can be performed. Formation of either the pyrrole or the furan derivative is pH- and regioisomer-structure-dependent. The results obtained, together with previous B3LYP calculations, support mechanistic proposals which suggest that pyrrole, or furan, formation proceeds via oxazine formation, followed by a boryl rearrangement and an intramolecular addition-elimination sequence.

19.
Org Biomol Chem ; 13(17): 4940-52, 2015 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-25812481

RESUMO

The simple octyl ß-D-galactofuranoside was previously described as a good bacteriostatic agent against Mycobacterium smegmatis, a non-pathogenic model of M. tuberculosis. In order to decipher its mechanism of action, STD NMR on whole M. smegmatis cells was implemented. It outlined the crucial role of the alkyl chain and the possibility of modulation on the furanosyl entity. Then, 16 new alkyl furanosides were synthesized in order to optimize the mycobacteriostatic activity. They all present the pending alkyl chain in a 1,2-trans configuration relative to the sugar ring. Three families were studied that differ by a substituent on the primary position of the galactofuranose ring, the series or the pending alkyl chain. Four of these neofuranosides showed growth inhibition inferior to the parent octyl ß-D-galactofuranoside. Double alkyl chains at C-1 and a polar substituent on the primary position of the furanoside significantly favored the activity. Finally, a mixed biantennary alkyl/aryl ß-D-galactofuranoside exhibited the best growth inhibition concentration at 90 µM.


Assuntos
Antibacterianos/farmacologia , Galactosídeos/farmacologia , Mycobacterium smegmatis/efeitos dos fármacos , Antibacterianos/química , Relação Dose-Resposta a Droga , Galactosídeos/química , Testes de Sensibilidade Microbiana , Estrutura Molecular , Mycobacterium smegmatis/crescimento & desenvolvimento , Estereoisomerismo , Relação Estrutura-Atividade
20.
Chemistry ; 20(44): 14518-23, 2014 Oct 27.
Artigo em Inglês | MEDLINE | ID: mdl-25212967

RESUMO

We describe a highly diastereoselective approach to anti-homoallylic alcohols from allylbenzene derivatives and aldehydes. The strategy is based on a cross-metathesis/isomerization/allylboration sequence catalyzed successively by ruthenium and iridium. This methodology provides another way to access this class of compounds, which leads to the preparation of hitherto-unknown homoallylic alcohols without the requirement to control the stereochemistry of the 1-alkenyl boronate intermediates. Our study towards an enantioselective version of this sequential reaction is also reported.

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