0000000001310423
AUTHOR
Miguel A. Maestro
Gold catalyzed stereoselective tandem hydroamination–formal aza-Diels–Alder reaction of propargylic amino esters
A gold-catalyzed tandem intramolecular hydroamination-formal aza-Diels-Alder reaction of propargylic amino esters is described. The overall process leads to the formation of a tetracyclic framework as a single diastereoisomer, with the creation of four bonds and five stereocenters.
Gold-Catalyzed Intramolecular Hydroamination of o-Alkynylbenzyl Carbamates: A Route to Chiral Fluorinated Isoindoline and Isoquinoline Derivatives
Enantiomerically pure fluorinated isoindoline and dihydroisoquinoline scaffolds have been prepared through a diastereoselective addition of fluorinated nucleophiles to Ellman’s N-(tert-butanesulfinyl)imines followed by a sequence of Sonogashira cross-coupling/gold(I)-catalyzed cycloisomerization of the corresponding carbamate. A more favored 5-exo-dig mechanism was observed mainly due to an electronic effect of the fluorinated group.
ChemInform Abstract: Gold Catalyzed Stereoselective Tandem Hydroamination-Formal Aza-Diels-Alder Reaction of Propargylic Amino Esters.
The overall sequence of the tandem reaction presented here leads to nitrogen-containing tetracycles under formation of 4 bonds and five stereocenters, in most cases as single diastereoisomers.
ChemInform Abstract: An Approach to 2,4-Substituted Pyrazolo[1,5-a]pyridines and Pyrazolo[1,5-a]azepines by Ring-Closing Metathesis.
Based on the title approach, the diastereoselective synthesis of potential peptidomimetics [(XI) and (XIV)] is described.
ChemInform Abstract: Intramolecular Michael Reaction of tert-Butylsulfinyl Ketimines: Asymmetric Synthesis of 3-Substituted Indanones.
The reaction proceeds in the presence of the Ruppert—Prakash reagent (Tms-CF3) with either TBAT or TBAF as a base.
Structure, magnetic properties and nuclease activity of pyridine-2-carbaldehyde thiosemicarbazonecopper(II) complexes.
New complexes of formulae [Cu(HL 2 )(H 2 O)(NO 3 )](NO 3 ) ( 1 ), [{Cu(L 1 )(tfa)} 2 ] ( 2 ), [{Cu(L 1 )} 2 (pz)](ClO 4 ) 2 ( 3 ) and {[{Cu(L 1 )} 2 (dca)](ClO 4 )} n ( 4 ), where HL 1 = pyridine-2-carbaldehyde thiosemicarbazone, HL 2 = pyridine-2-carbaldehyde 4 N -methylthiosemicarbazone, Htfa = trifluoroacetic acid (CF 3 COOH), pz = pyrazine (C 4 H 4 N 2 ) and dca = dicyanamide [N(CN) 2 ] − , have been synthesized and characterized. The crystal structures of these compounds are built up of monomers ( 1 ), dinuclear entities with the metal centers bridged through the non-thiosemicarbazone coligand ( 2 and 3 ) and 1D chains of dimers ( 4 ). In all the cases, square–pyramidal copper(II) io…
Base-Dependent Stereodivergent Intramolecular Aza-Michael Reaction: Asymmetric Synthesis of 1,3-Disubstituted Isoindolines
The nucleophilic addition (A(N)) / intramolecular aza-Michael reaction (IMAMR) process on Ellman's tert-butylsulfinyl imines, bearing a Michael acceptor in the ortho position, is studied. This reaction affords 1,3-disubstituted isoindolines with a wide range of substituents in good yields and diastereoselectivities. Interestingly, careful choice of the base for the aza-Michael step allows either the cis or the trans diastereoisomers to be exclusively obtained. This stereodivergent cyclization has enabled the synthesis of C2-symmetric bisacetate-substituted isoindolines. In addition, bisacetate isoindolines bearing two well-differentiated ester moieties are also noteworthy because they may a…
(1,3,4‐Oxadiazole)copper(II) Compounds: Dimensionality, Magnetism and Nuclease Activity
The work presented here describes the synthesis of new copper(II) complexes derived from 2-amino-5-(pyridin-2-yl)-1,3,4-oxadiazole (L1) and 2-methylamino-5-(pyridin-2-yl)-1,3,4-oxadiazole (L2) which also incorporate azido (N3 -), thiocyanato (NCS-), cyanato (NCO-), dicyanamido [N(CN)2 -, dca] and malonato (C3H2O4 2-, mal) coligands. Structures of the [Cu(L2)(mal)(H2O)]·2H 2O(1), [{Cu(L2)(mal)}2] (2), [Cu(L 2)2-(NCS)2] (3), [Cu(L1)(NCS) 2]n (4) and [{Cu(L2)}2(dca) 2](ClO4)2·2H2O (5) compounds show the dependence of the dimensionality on parameters such as the type of oxadiazole and coligand utilised, solvents or reaction times. In this sense, 1 and 3 are mononuclear complexes, 2 contains cen…
ChemInform Abstract: Gold-Catalyzed Intramolecular Hydroamination of o-Alkynylbenzyl Carbamates: A Route to Chiral Fluorinated Isoindoline and Isoquinoline Derivatives.
Title compounds are prepared in enantiomerically pure form by the diastereoselective addition of fluorinated nucleophiles to N-(tert-butanesulfinyl)imines (I) followed by a sequence of Sonogashira cross-coupling/gold(I)-catalyzed cycloisomerization of the corresponding carbamate.
Intramolecular Michael reaction of tert-butylsulfinyl ketimines: asymmetric synthesis of 3-substituted indanones.
Aromatic tert-butylsulfinyl ketimines bearing a suitable Michael acceptor at the ortho position readily undergo an intramolecular conjugate addition achieving indanone derivatives in good yields and complete diastereoselectivity.
ChemInform Abstract: Base-Dependent Stereodivergent Intramolecular Aza-Michael Reaction: Asymmetric Synthesis of 1,3-Disubstituted Isoindolines.
For the reaction of the compounds (I) the careful choice of the base allows the exclusive formation of either cis or trans diastereoisomer with the exception of the trihalogenates (Ie) and (If), which afford the cis-products regardless of the base used.
An Approach to 2,4-Substituted Pyrazolo[1,5-a]pyridines and Pyrazolo[1,5-a]azepines by Ring-Closing Metathesis
The ring-closing metathesis (RCM) reactions of dienylpyrazoles have been employed in the synthesis of pyrazolo[1,5-a]pyridine and pyrazolo[1,5-a]azepine derivatives. Based on this approach, the diastereoselective synthesis of potential peptidomimetics containing four amino acid residues with the second (i+1) and third (i+2) fragments having been substituted by bicyclic frameworks is described.
CCDC 841484: Experimental Crystal Structure Determination
Related Article: Santos Fustero, Raquel Román, Amparo Asensio, Miguel A. Maestro, José L. Aceña, Antonio Simón-Fuentes|2013|Eur.J.Org.Chem.|2013|7164|doi:10.1002/ejoc.201300901
CCDC 941485: Experimental Crystal Structure Determination
Related Article: Santos Fustero, Raquel Román, Amparo Asensio, Miguel A. Maestro, José L. Aceña, Antonio Simón-Fuentes|2013|Eur.J.Org.Chem.|2013|7164|doi:10.1002/ejoc.201300901
CCDC 916244: Experimental Crystal Structure Determination
Related Article: Santos Fustero, Ignacio Ibáñez, Pablo Barrio, Miguel A. Maestro, Silvia Catalán|2013|Org.Lett.|15|832|doi:10.1021/ol3035142
CCDC 935857: Experimental Crystal Structure Determination
Related Article: Santos Fustero, Lidia Herrera, Ruben Lázaro, Elsa Rodríguez, Miguel A. Maestro, Natalia Mateu, Pablo Barrio|2013|Chem.-Eur.J.|19|11776|doi:10.1002/chem.201301591
CCDC 916245: Experimental Crystal Structure Determination
Related Article: Santos Fustero, Ignacio Ibáñez, Pablo Barrio, Miguel A. Maestro, Silvia Catalán|2013|Org.Lett.|15|832|doi:10.1021/ol3035142