A5053501208- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Crystallography and molecular interactions
- Organometallic Complex Synthesis and Catalysis
- Metal complexes synthesis and properties
- Chemical Synthesis and Analysis
- Fluorine in Organic Chemistry
- Catalytic Cross-Coupling Reactions
- Catalytic C–H Functionalization Methods
- Magnetism in coordination complexes
- Synthetic Organic Chemistry Methods
- Coordination Chemistry and Organometallics
- Asymmetric Hydrogenation and Catalysis
- Catalytic Alkyne Reactions
- Inorganic Chemistry and Materials
- Molecular Sensors and Ion Detection
- Synthesis and Biological Evaluation
- Asymmetric Synthesis and Catalysis
- Ferrocene Chemistry and Applications
- Synthesis and Reactions of Organic Compounds
- Organometallic Compounds Synthesis and Characterization
- Metal-Organic Frameworks: Synthesis and Applications
- Luminescence and Fluorescent Materials
- Synthesis and Catalytic Reactions
- Cyclopropane Reaction Mechanisms
ORFEO-CINQA Research Network
2015-2023
Universitat de València
2014-2023
Instituto de Química Orgánica General
2017-2022
Center for Innovation
2020
Instituto Valenciano de la Edificación
2019
Centro Médico Sanitas Valencia
2015
Universidad Complutense de Madrid
2015
Universitat Autònoma de Barcelona
2010
Universidad de Murcia
1990-2009
Centro de Investigacion Principe Felipe
2007-2009
1,3-Di(2-pyridyl)benzene undergoes regioselective orthometalation with Pd(OAc)2 on the central aryl ring, giving rise to a dimeric complex in which four acetate units act as bridges between two doubly metalated ligands and each pyridine ligand coordinates different metal atom. The reaction chloride-containing Pd(II) complexes does not lead C−H activation but coordination without Pd−C bonds. Cycloplatination of 1,3-di(2-pyridyl)benzene takes place at C-2 benzene generating terdentate ligand....
Insertion of CO into 2-aminophenylpalladium complexes leads to 2-aminobenzoylpalladium derivatives. When these compounds are forced coordinate a carbon donor and phosphane ligand in the trans position, C−P coupling process or an insertion oxygen occurs (see scheme). In this case, dinuclear palladium complex containing bridging anthranilato is isolated.
By the refluxing of an acetonitrile solution [Pd(OAc)2]3 and primary amines 4-XC6H4CH2NH2 (F, Cl, NO2, OMe), 3,5-X2C6H3CH2NH2 (X = or PhCH2CH2NH2 (Pd:amine 1:1) subsequent addition excess NaBr, corresponding orthometalated complexes [Pd{C6H3(CH2NH2)-2,X-5}(μ-Br)]2, [Pd{C6H3(CH2NH2)-2,(OMe)2-4,6}(μ-Br)]2, [Pd{C6H3(CH2NH2)-2}(μ-Br)]2 are obtained. Alternatively, hydrochloride F, NO2) can also be used to prepare [Pd{C6H3(CH2NH2)-2,X-5}(μ-Cl)]2 complexes. These results show that benzylamines...
Abstract The synthesis, electrochemical, and optical properties of a new [3.3]ferrocenophane framework in which two ferrocene subunits, with similar electronic environments, are linked through substituted guanidine moieties, reported. receptors 4 – 7 have been prepared good yields by the reaction bis(carbodiimide) 3 primary amines. This architecture is exceptionally “tunable” because variety “legs” may be appended to basic scaffold give wide range signaling units. These show remarkable...
The competition between π- and dual σ,π-gold-activation modes is revealed in the gold(I)-catalyzed heterocyclization of 1-(o-ethynylaryl)urea. A noticeable effect various ligands gold complexes on choice these activation described. cationic [Au(IPr)](+) (IPr=2,6-bis(diisopropylphenyl)imidazol-2-ylidene) complex cleanly promotes π terminal alkynes, whereas [Au(PtBu3 )](+) favors intermediate σ,π species. In this experimental mechanistic study, which includes kinetic cross-over experiments,...
Carbodiimides and suitably activated α,β-unsaturated carboxylic acids react effectively to afford a vast array of 1,3,5-trisubstituted hydantoins by means regiospecific domino condensation/aza-Michael/N→O acyl migration. The reaction works well in very mild conditions (20 °C, dichloromethane) with fumaric acid derivatives bearing an electron-withdrawing group the β position. Good results have been obtained also less substrates only one position, using more polar solvents (acetonitrile, DMF),...
3-Substituted 1-(o-ethynylaryl)ureas 1 selectively undergo either 6-exo-dig or 5-endo-dig cyclization (to give 4-methylene-3,4-quinazolin-2-ones 2 indoles 3, respectively) depending on the choice of metal, ligand, and reaction conditions. The best results (up to 96% yield) in preparation hydroamination products are achieved with highly bulky NHC-stabilized cationic gold(I) complex [Au(IPr)](+). Conversely, ureas bearing an internal alkyne lead mode regardless employed. Whereas nature...
Direct oxidative Kita-type coupling between naphthalene and substituted benzenes was found to proceed via four-component coupling, leading a linear tetraarene with binaphthalene core. The methodology extendable the of unfunctionalized 1,1'-binaphthalene mesitylene give hexaarene product in remarkably chemoselective manner 87% yield. method represents an attractive alternative traditional syntheses related oligonaphthalene products sequence metal-catalyzed cross-coupling steps.
The ferrocene-triazole derivative 4, available from 1,1'-bis(diazido)ferrocene by sequential functionalization through click-type chemistry and the Staudinger reaction, is elaborated as a lab-on-a-molecule for selective sensing of HP(2)O(7)(3-) Hg(2+). Receptor 4 behaves ratiometric fluorescent probe with good selectivity over other anions, whereas in presence Hg(2+) it modifies emission pyrene unit, acting on-off sensor low detection limit. most salient feature compound its behavior an...
The Sc(OTf)3-catalyzed [3 + 2]-annulation reaction between cyclopropenones and donor–acceptor cyclopropanes is described. process leads directly to the formation of 4-oxaspiro[2.4]hept-1-ene derivatives in good excellent yields. Density functional theory calculations suggest that pathway strongly preferred over possible 3]-process.
Abstract Several bis‐triazolium‐based receptors have been synthesized and their anion‐recognition capabilities studied. The central chiral 1,1′‐bi‐2‐naphthol (BINOL) core features either two aryl or ferrocenyl end‐capped side arms with halogen‐ hydrogen‐bonding triazolium receptors. NMR spectroscopic data indicate the simultaneous occurrence of several charge‐assisted aliphatic heteroaromatic C−H noncovalent interactions combinations hydrogen halogen bonding. are able to selectively interact...
The application of organoboron compounds as light-absorbing or light-emitting species in areas relevant organic electronics biomedicine has motivated the search for new materials which contribute to progress those applications. This article reports synthesis four-coordinate boron complexes based on unexplored 7-(azaheteroaryl)indole ligands. An easy synthetic approach enabled fine-tuning electronic structure by modifying a heteroaromatic component conjugated system. Furthermore,...
Mixtures of "Pd(dba)2" (dba = dibenzylideneacetone) and 2,2'-bipyridine (bpy; 1:2) or N,N,N',N'-tetramethylethylenediamine (tmeda; 1:1) react with 2-bromo-4-nitroaniline to give [Pd{C6H3NH2-2-NO2-5}Br(N−N)] (N−N bpy (1b), tmeda (1b')). Reactions 2-iodoaniline mixtures isonitriles RNC (R C6H3Me2-2,6 (Xy), 2:1:2 molar ratios; R tBu, 2.9:1:2 ratios) result in the formation complexes [Pd{κ2C,N-C(NXy)C6H4NH2-2}I(CNXy)] (2a) trans-[Pd{C(NtBu)C6H4NH2-2}I(CNtBu)2] (3a*). The reactions...
By refluxing of dibenzylamine and [Pd(OAc)2]3 (3.2:1) in acetone, the orthometalated complex [Pd{C6H4(CH2NHCH2Ph)-2}(μ-OAc)]2 (1) is obtained. Metathetical reaction 1 with NaBr affords corresponding bromo-bridging dimer [Pd{C6H4(CH2NHCH2Ph)-2}(μ-Br)]2 (2). Neutral ligands split bromo bridge to give monomeric complexes [Pd{C6H4(CH2NHCH2Ph)-2}Br(L)] [L = PPh3, (3a), NH(CH2Ph)2 (3b)]. Complexes [Pd{C6H4(CH2NHCH2Ph)-2}(acac)] (4) or [Pd{C6H4(CH2NHCH2Ph)-2}L2]ClO4 py (5a), L2 1,5-cyclooctadiene...
The mercuriation of 3,4,5-trimethoxy(N-tert-butylcarbamoyl)benzene with mercury(II) acetate and subsequent reaction KCl leads to the formation [Hg{C6H{C(O)NHBut}-6-(OMe)3-2,3,4}Cl] (1), which is symmetrized [NMe4]Cl give [Hg{C6H{C(O)NHBut}-6-(OMe)3-2,3,4}2] (2). 2 [PdCl2(MeCN)2] 2,2'-bipyridine (bpy) affords [Pd(C6H{C(O)NHBut}-6-(OMe)3-2,3,4)Cl(bpy)] (3), reacts Tl(CF3SO3) Complex acetylenes RC⋮CR metallic palladium spirocyclic compound...
Abstract Partially modified retro‐ (PMR) and retro‐inverso (PMRI) ψ[NHCH(CF 3 )]Gly peptides, a conceptually new class of peptidomimetics, have been synthesized in wide structural diversity variable length by aza‐Michael reaction enantiomerically pure α‐amino esters peptides with geometrically N ‐4,4,4‐trifluorocrotonoyl‐oxazolidin‐2‐ones. The factors underlying the observed moderate to good diastereocontrol investigated. conformations model PMR‐ψ[NHCH(CF tripeptides studied solution 1 H NMR...
Reaction of the iminophosphorane Ph3PNC6H4Me-4 (1a) with Hg(OAc)2 and LiCl gives mercurated [Hg{C6H3(NPPh3)-2-Me-5}Cl] (2). The latter reacts NaBr to give [Hg{C6H3(NPPh3)-2-Me-5}Br] (3). 2 MeC6H4NCO-4 or CX2 (X = O, S) [Hg{C6H3(NCNC6H4Me-4')-2-Me-5}Cl] (4) [Hg{C6H3{NCNC6H3(HgCl)-1'-Me-5'}-2-Me-5}Cl] (5), respectively. Iminophosphoranes Ph3PNC6H4R-4 (1b) react Pd(OAc)2 complexes [Pd{κ2-C,N-C6H4(PPh2NC6H4R-4')-2}(μ-OAc)]2 (R Me (6a), MeO (6b)), in which palladation takes place at one phenyl...
Racemic and chiral nonracemic α-substituted α-unsubstituted β-fluoroalkyl β-amino acid derivatives 6 9 have been synthesized in two steps starting from fluorinated imidoyl chlorides 1 ester enolates. This approach is based on the chemical reduction of previously obtained γ-fluorinated β-enamino esters 4 by using ZnI2/NaBH4 a nonchelated aprotic medium (dry CH2Cl2) as reducing agent. A metal-chelated six-membered model has suggested to explain stereochemical outcome reaction. The process...
Palladium-catalyzed C--C bond formation involving secondary sp3-hybridized carbon is described. These reactions occur with 1-bromoethyl arylsulfoxides and different arylboronic acids, to produce the corresponding arylated sulfoxides in moderate high yields complete stereospecificity. Despite presence of beta hydrogens substrate, competitive beta-hydride elimination not a significant side reaction when coordinating solvents are used. The reported cross-coupling involves C(sp3)--C(sp2)...
The ortho-metalated complex [Pd2{κ2(C,N)-C6H4CH2CH2NHMe-2}2(μ-Br)2] (1) can be prepared by refluxing a 1:1 mixture of Pd(OAc)2 and N-methylphenethylamine in acetonitrile, followed addition an excess NaBr. Complex 1 reacts with PPh3 to give the mononuclear derivative [Pd{κ2(C,N)-C6H4CH2CH2NHMe-2}Br(PPh3)] (2). cationic [Pd{κ2(C,N)-C6H4CH2CH2NHMe-2}(py)2]ClO4 (3) obtained reacting AgClO4 pyridine. previously reported [Pd2{κ2(C,N)-C6H4CH2NHCH2Ph-2}2(μ-Br)2] (A) PhC≡CCO2R (R = Me, Et)...
The complexes [Pd(C6H4X-2)BrL2] (L2 = trans-(PR3)2, R Ph, X CHCH2 (1a), CHO (1b), C(O)Me (1c), CN (1d); p-To 4-tolyl, (1a'); L2 bpy 2,2'-bipyridine, (2b), (2c), (2d); tmeda N,N,N',N'-tetramethylethylenediamine, (2b'), (2d')) have been prepared by oxidative addition of the corresponding bromoarene BrC6H4X-2 to "Pd(dba)2" (=[Pd2(dba)3]·dba, dba dibenzylideneacetone) in presence appropriate ligand. compound [Pd{C6H4(CHCH2)-2}(bpy)(PPh3)]TfO (3a; TfO CF3SO3) has obtained reacting 1a with TlOTf....
The reactions of Q[Au(acac)2] (Q = N(PPh3)2 (PPN; a), NPr4 (b); acac acetylacetonato) with terminal alkynes the type HC⋮CC6H4R-4 in a 1:2 molar ratio affords complexes Q[Au(C⋮CC6H4R-4)2] (R NO2 (1), C6H4NO2-4 (2), (E)-CHCHC6H4NO2-4 (3)). same react [AuCl(CNBut)] NEt3 to give [Au(C⋮CC6H4R-4)(CNBut)] (4), (5), (6)). When NHEt2 is used instead NEt3, attack secondary amine at isonitrile ligand takes place and alkynyl carbene [Au(C⋮CC6H4R-4){C(NHBut)(NEt2)}] (7), (8), (9)) are obtained. crystal...
The organomercurials [HgCl{C6H3(CHO)2-2,5}] (1) and [Hg{C6H3(CHO)2-2,5}2] (2) have been prepared by mercuriation of terephthaldehyde. Palladium complexes [PdCl{C6H3(CHO)2-2,5}(N-N)] (N-N = N,N,N',N'-tetramethylethylenediamine (tmeda) (3) or 2,2'-bipyridine (bpy) (3')) trans-[PdCl{C6H3(CHO)2-2,5}(PPh3)2]·H2O (4) obtained reacting (Me4N)2[Pd2Cl6] trans-[PdCl2(PPh3)2], respectively, with 1 2. reaction potassium permanganate 3 3' mercurial results in the selective oxidation 5-formyl substituent...
When H2N(CH2)2C6H4OMe-4 (RNH2) and Pd(OAc)2 are reacted in a 2:1 molar ratio, the complex [Pd(OAc)2(NH2R)2] (1) is obtained. Complex 1 reacts with equiv of to give dinuclear [Pd(OAc)(μ-OAc)(NH2R)]2 (2). 2 heated acetonitrile at 80 °C, ortho-metalated [Pd{C6H3(CH2)2NH2-2-OMe-5-κ2C,N}(μ-OAc)]2 (3a) 3a also prepared by refluxing RNH2 1:1 ratio acetonitrile. NaBr or LiCl afford complexes [Pd{C6H3(CH2)2NH2-2-OMe-5-κ2C,N}(μ-X)]2 (X = Cl (3b), Br (3c)). PPh3 splits acetate halide bridge 3b...