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1. α-(Aminomethyl)acrylates as acceptors in radical–polar crossover 1,4-additions of dialkylzincs: insights into enolate formation and trapping

Author

Angel Palillero-Cisneros, Paola G. Gordillo-Guerra, Fernando García-Alvarez, Olivier Jackowski, Franck Ferreira, Fabrice Chemla, Joel L. Terán, and Alejandro Perez-Luna

Subjects
β-amino acids, tandem reactions, radical–polar crossover, tert-butanesulfinamide, zinc radical transfer, Science, Organic chemistry, QD241-441
Abstract

We demonstrate that α-(aminomethyl)acrylates are suitable acceptors for 1,4-additions of dialkylzincs in aerobic conditions. The air-promoted radical–polar crossover process involves the 1,4-addition of an alkyl radical followed by homolytic substitution at the zinc atom of dialkylzinc. Coordination of the nitrogen atom to zinc enables this SH2 process which represents a rare example of alkylzinc-group transfer to a tertiary α-carbonyl radical. The zinc enolate thus formed readily undergoes β-fragmentation unless it is trapped by electrophiles in situ. Enolates of substrates having free N–H bonds undergo protodemetalation to provide ultimately the 1,4-addition adduct. In the presence of carbonyl acceptors, aldol condensation occurs providing overall a tandem 1,4-addition–aldol process. When a tert-butanesulfinyl moiety is present on the nitrogen atom, these electrophilic substitution reactions occur with good levels of chiral induction, paving the way to enantioenriched β2-amino acids and β2,2-amino acids.

Published
2023
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2. Modular synthesis of 2-furyl carbinols from 3-benzyldimethylsilylfurfural platforms relying on oxygen-assisted C–Si bond functionalization

Author

Sebastien Curpanen, Per Reichert, Gabriele Lupidi, Giovanni Poli, Julie Oble, and Alejandro Perez-Luna

Subjects
biomass, copper, cyclic siloxanes, 2-furyl carbinols, silicon, Science, Organic chemistry, QD241-441
Abstract

3-Silylated furfurals, readily prepared in three steps from biomass-derived furfural and 5-methylfurfural, are converted into 3-silylated 2-furyl carbinols upon condensation with organomagnesium or organolithium reagents. The hydroxy unit of the carbinol adducts can be exploited to promote C3(sp2)–Si bond functionalization through intramolecular activation. Two approaches were contemplated for this purpose. Activation by alkoxides of the C3–SiEt3 or C3–SiMe2t-Bu bonds was ineffective. Conversely, treatment of the C3-benzyldimethylsilyl-appended derivatives with tetrabutylammonium fluoride led to cyclic siloxanes, which revealed to be competent donors for copper-catalyzed cross-coupling reactions, such as arylation reactions catalyzed by Pd2(dba)3/CuI, as well as allylation and methylation reactions catalyzed by CuI⋅PPh3. C3-Benzyldimethylsilyl-appended furfurals are thus introduced as versatile platforms, providing a modular access to 3-substituted 2-furyl carbinols from renewable feedstock.

Published
2022
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3. tert-Butanesulfinamides as Nitrogen Nucleophiles in Carbon–Nitrogen Bond Forming Reactions

Author

Johana Ramirez Hernandez, Fabrice Chemla, Franck Ferreira, Olivier Jackowski, Julie Oble, Alejandro Perez-Luna, and Giovanni Poli

Subjects
Amination, Tert-butanesulfinamide, Chiral nucleophiles, Chemistry, QD1-999
Abstract

The use of tert-butanesulfinamides as nitrogen nucleophiles in carbon–nitrogen bond forming reactions is reviewed. This field has grown in the shadow of the general interest in N-tert-butanesulfinyl imines for asymmetric synthesis and occupies now an important place in its own right in the chemistry of the chiral amine reagent tert-butanesulfinamide. This article provides an overview of the area and emphasizes recent contributions wherein the tert-butanesulfinamides act as chiral auxiliaries or perform as nitrogen donors in metal-catalyzed amination reactions.

Published
2016
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7. C3–H Silylation of Furfural Derivatives: Direct Access to a Versatile Synthetic Platform Derived from Biomass

Author

Sébastien Curpanen, Giovanni Poli, Alejandro Perez-Luna, and Julie Oble

Abstract

The sustainable production of industry-relevant chemicals, ranging from biofuels to pharmaceuticals, requires the development of efficient functionalization of biomass-derived building blocks, such as furan derivatives. Herein we report directed iridium-catalyzed C3–H silylation of furfural compounds, which grants access to versatile synthetic platforms. This transformation was developed on furfuryl derivatives, using imines as directing groups, and trialkylsilanes or bis(trimethylsilyl)methylsilane as silylating agents, in the presence of a hydride scavenger. Subsequently, fluoride-mediated activation strategies were applied to the C3–SiMe(OSiMe3)2 furfural derivatives. This strategy enables a wide range of transformations, namely arylation, alkenylation, alkynylation, allylation and alkylation, as well as halogenation and trifluoromethylation. A variety of high value-added products were thus easily obtained from the same common C3-silylated furfural platform.

Published
2022

8. Radical Germylzincation of Aryl- and Alkyl-Substituted Internal Alkynes

Author

Franck Ferreira, Karen de la Vega-Hernández, Fabrice Chemla, Alejandro Perez-Luna, Olivier Jackowski, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Aryl, Organic Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, Hydrocarbons, 0104 chemical sciences, Electrophilic substitution, chemistry.chemical_compound, Electromagnetic radiation, Alcohols, [CHIM]Chemical Sciences, Molecule, Selectivity, Stereoselectivity, Physical and Theoretical Chemistry, Molecular structure, Alkyl
Abstract

International audience; The stereoselective germylzincation of internal alkynes delivering trisubstituted vinylgermanes is achieved via a radical chain process involving Ph3GeH and Et2Zn with AIBN as initiator. Excellent levels of regiocontrol are observed for non-symmetric (aryl, alkyl)-substituted alkynes, as well as for propargylic alcohols with aryl-, alkyl-, or silyl-substituted alkynes. The germylzincation reaction can be combined in one pot with the Cu(I)-mediated electrophilic substitution of the C(sp 2)-Zn bond to obtain synthetically challenging tetrasubstituted vinylgermanes.

Published
2021

9. C(sp 2 )−Si Bond Functionalization through Intramolecular Activation by Alkoxides

Author

Sebastien Curpanen, Giovanni Poli, Alejandro Perez-Luna, Julie Oble, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Organic Chemistry, Silyl migration, Brook rearrangement, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Synthetic methods, Intramolecular force, Polymer chemistry, Hiyama cross-coupling, Surface modification, [CHIM]Chemical Sciences, Anion Relay Chemistry, Physical and Theoretical Chemistry
Abstract

International audience; This minireview covers recent progress in the functionalization of C(sp2)−Si bonds by intramolecular activation by alkoxides. Such processes involve the formation of a cyclic hypervalent silicon intermediate that allows carbon‐to‐oxygen migration of the organosilyl group and thus the formation of a carbanionic species poised to undergo electrophilic substitution. The C(sp2)−Si bond cleavage can be “endocyclic” (Brook rearrangement) or “exocyclic”. Organosilicon reagents are invaluable tools in the hands of the modern chemist that allow accomplishing a number of synthetically useful transformations. While some are standard reactions, others are more complex transformations, such as the Brook rearrangement and its variants. This carbon‐to‐oxygen silyl migration represents a privileged method to generate transient carbanionic species well suited to undergo functionalization upon electrophilic substitution in the presence of an electrophile. This minireview focuses on recent advances in C(sp2)−Si bond functionalization through intramolecular activation by alkoxides. The key elements of reactivity will be highlighted in the introduction to allow the proper understanding of the migration process. Then, an overview of the reactivity of substrates incorporating the C(sp2)−Si motif and their synthetic applications will be provided.

Published
2021

10. Development of a Radical Silylzincation of (Het)Aryl-Substituted Alkynes and Computational Insights into the Origin of the trans-Stereoselectivity

Author

Fabrice Chemla, Karen de la Vega-Hernández, Hélène Gérard, Martin Oestreich, Juan Sanz García, Stéphanie Halbert, Alejandro Perez-Luna, Carolin Fopp, Olivier Jackowski, Frédéric Guégan, Franck Ferreira, Elise Romain, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie théorique (LCT), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut für Chemie [TUB Berlin], and Technische Universität Berlin (TU)

Subjects
Vinylsilanes, 010405 organic chemistry, Chemistry, Stereochemistry, Radical reactions, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Aryl, chemistry.chemical_element, Silylmetalation, General Chemistry, Zinc, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Stereoselectivity, Silylzinc reagents
Abstract

International audience; Aryl- and hetaryl-substituted acetylenes undergo regio- and stereoselective silylzincation by reaction with [(Me3Si)3Si]2Zn in the presence of Et2Zn (10–110 mol%) as additive. The distinctive feature of this addition across the C−C triple bond is its trans stereoselectivity. The radical nature of the silylzincation process is supported by diagnostic experiments and DFT calculations, which also corroborate the role played by steric effects to obtain that stereoselectivity. The procedure can be combined in one-pot with the copper(I)-mediated electrophilic substitution of the C(sp2)−Zn bond, with retention of the double bond geometry. This makes it valuable for the synthesis of stereodefined di- and trisubstituted vinylsilanes.

Published
2021

11. Domino Methylenation/Hydrogenation of Aldehydes and Ketones by Combining Matsubara's Reagent and Wilkinson's Catalyst

Author

Kevin Gervais, Alejandro Perez-Luna, Olivier Jackowski, Raoudha Abderrahim, Radhouan Maazaoui, Fabrice Chemla, Franck Ferreira, and María Pin-Nó

Subjects
010405 organic chemistry, Chemistry, Organic Chemistry, Noyori asymmetric hydrogenation, 010402 general chemistry, 01 natural sciences, Domino, Wilkinson's catalyst, 0104 chemical sciences, chemistry.chemical_compound, Cascade reaction, Reagent, Organic chemistry, Domino process, Physical and Theoretical Chemistry, Chemoselectivity, Methyl group
Abstract

The methylenation/hydrogenation cascade reaction of aldehydes or ketones through a domino process involving two ensuing steps in a single pot is realized. The compatibility of Matsubara's reagent and Wilkinson's complex give a combination that allows, under dihydrogen, the transformation of a carbonyl function into a methyl group. This new method is suitable to introduce an ethyl motif from aromatic and aliphatic aldehydes with total chemoselectivity and total retention of α-stereochemical purity. The developed procedure is also extended to the introduction of methyl groups from ketones.

Published
2016

12. Catalytic Chemo and Stereoselective Semi-Hydrogenation of Alkynes to E-Alkenes Using the Combination of Pd catalyst and ZnI 2

Author

Radhouan Maazaoui, Fabrice Chemla, Olivier Jackowski, Alejandro Perez-Luna, Raoudha Abderrahim, Franck Ferreira, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and Université de Carthage - University of Carthage

Subjects
010405 organic chemistry, Chemistry, Organic Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, Catalysis, Reaction temperature, Reagent, [CHIM]Chemical Sciences, Stereoselectivity, Physical and Theoretical Chemistry, Isomerization
Abstract

International audience; An efficient E-selective semihydrogenation of internal alkynes was developed under low dihydrogen pressure and low reaction temperature from commercially available reagents: Cl2Pd(PPh3)2, Zn 0 and ZnI2. Kinetic studies and control experiments underline the significant role of ZnI2 in this process under H2 atmosphere, establishing that the transformation involves syn-hydrogenation followed by isomerization. This simple and easy-to-handle system provides a route to E-alkenes under mild conditions.

Published
2018

14. Synthesis of allenylzinc reagents by 1,2-rearrangement of alkynyl(disilyl)zincates derived from acetylenic epoxides and acetylenic aziridines

Author

Laurent Debien, Fabrice Chemla, Valentin N. Bochatay, Olivier Jackowski, Franck Ferreira, Alejandro Perez-Luna, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Réactivité organométallique et catalyse pour la synthèse (ROCS), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Chemistry(all), 010405 organic chemistry, Metalation, General Chemical Engineering, chemistry.chemical_element, General Chemistry, Aziridine, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, chemistry.chemical_compound, 1,2-rearrangement, chemistry, Reagent, Chemical Engineering(all), Organic chemistry, [CHIM]Chemical Sciences, Lithium, ComputingMilieux_MISCELLANEOUS
Abstract

Lithium alkynyl(disilyl)zincates obtained from metalated ethynyloxiranes, as well as from N - tert -butanesulfinyl(ethynyl)aziridines or N - tert -butanesulfonyl(ethynyl)aziridines, undergo 1,2-migration of the organosilyl group with ring opening of the oxirane or aziridine ring by S N i displacement. A developed protocol that involves n BuLi for the metalation step offers a straightforward approach to the corresponding δ-oxy- and δ-amino α-silyl allenylzinc intermediates. The reagents derived from the epoxides are amenable to subsequent in situ condensation with aldehydes or ketones to provide 1,3-diols but not those derived from aziridines that only react sluggishly in similar condensations.

Published
2017

15. Reactivity of tert-butanesulfinamides in palladium-catalyzed allylic substitutions

Author

Guillaume Prestat, Laetitia Mistico, Giovanni Poli, Emel Ay, Julie Oble, Vaizanne Huynh, Fabrice Chemla, Alejandro Perez-Luna, Franck Ferreira, Aurelie Bourderioux, Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Chimie organique et bioorganique (COB), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Ecole Nationale Supérieure de Chimie de Mulhouse-Centre National de la Recherche Scientifique (CNRS), Réactivité organométallique et catalyse pour la synthèse (ROCS), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire ( IPCM ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Centre National de la Recherche Scientifique ( CNRS ), Chimie organique et bioorganique ( COB ), Université de Haute-Alsace (UHA) Mulhouse - Colmar ( Université de Haute-Alsace (UHA) ) -Ecole Nationale Supérieure de Chimie de Mulhouse-Centre National de la Recherche Scientifique ( CNRS ), Réactivité organométallique et catalyse pour la synthèse ( ROCS ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Centre National de la Recherche Scientifique ( CNRS ), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie organique et bioorganique (COB), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Substitution reaction, Allylic rearrangement, Chemistry, Organic Chemistry, Regioselectivity, chemistry.chemical_element, [ CHIM ] Chemical Sciences, Biochemistry, Medicinal chemistry, Inorganic Chemistry, chemistry.chemical_compound, Nucleophile, Sulfinamide, Materials Chemistry, [CHIM]Chemical Sciences, Reactivity (chemistry), Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, Amination, Palladium
Abstract

The performance of tert-butanesulfinamides as nitrogen nucleophiles in Pd(0)-catalyzed allylic substitution reactions has been investigated. Metalated N-alkyl and N-acetyl sulfinamides have been identified as suitable partners for the reaction with π-allyl–palladium complexes. The cross-coupling of N-acetyl tert-butanesulfinamide with 2- or 3-substituted linear allylic carbonates is achieved in the presence of Pd(OAc)2 (5 mol%) and dppe (7.5 mol%) and does not require an additional base. The reaction proceeds in high yields (59–98%) to produce the corresponding E-configured linear allylic sulfinamides in a totally regioselective and highly diastereoselective manner. The sulfur atom remains configurationally stable throughout the allylation process, and thus the coupling products are obtained in enantiomerically pure form.

Published
2014

16. tert-Butanesulfinamides as Nitrogen Nucleophiles in Carbon-Nitrogen Bond Forming Reactions

Author

Giovanni Poli, Alejandro Perez-Luna, Julie Oble, Johana Ramirez Hernandez, Fabrice Chemla, Olivier Jackowski, Franck Ferreira, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
General interest, 010405 organic chemistry, Enantioselective synthesis, chemistry.chemical_element, General Medicine, General Chemistry, CHIRAL NUCLEOPHILES, 010402 general chemistry, 01 natural sciences, Nitrogen, 0104 chemical sciences, chemistry.chemical_compound, Chemistry, AMINATION, chemistry, Nucleophile, Carbon–nitrogen bond, Reagent, Organic chemistry, [CHIM]Chemical Sciences, TERT-BUTANESULFINAMIDE, Chiral amine, QD1-999, Amination
Abstract

The use of tert-butanesulfinamides as nitrogen nucleophiles in carbon–nitrogen bond forming reactions is reviewed. This field has grown in the shadow of the general interest in N-tert-butanesulfinyl imines for asymmetric synthesis and occupies now an important place in its own right in the chemistry of the chiral amine reagent tert-butanesulfinamide. This article provides an overview of the area and emphasizes recent contributions wherein the tert-butanesulfinamides act as chiral auxiliaries or perform as nitrogen donors in metal-catalyzed amination reactions.

Published
2016

17. Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs

Author

Florian Dulong, Alejandro Perez-Luna, Fabrice Chemla, Franck Ferreira, Institut Parisien de Chimie Moléculaire (IPCM), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Radical, Dimethylzinc, carbozincation, chemistry.chemical_element, Zinc, 010402 general chemistry, Zinc atom, 01 natural sciences, Full Research Paper, lcsh:QD241-441, chemistry.chemical_compound, Cascade reaction, lcsh:Organic chemistry, Polymer chemistry, Organic chemistry, tandem reaction, lcsh:Science, Carbenoid, Alkyl, chemistry.chemical_classification, 010405 organic chemistry, carbometallation, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, radicals, 3. Good health, 0104 chemical sciences, Chemistry, chemistry, 13. Climate action, Stereoselectivity, lcsh:Q, carbenoids
Abstract

The formation of alkylidenezinc carbenoids by 1,4-addition/carbozincation of dialkylzincs or alkyl iodides based on zinc atom radical transfer, in the presence of dimethylzinc with β-(propargyloxy)enoates having pendant iodo- and bromoalkynes, is disclosed. Formation of the carbenoid intermediate is fully stereoselective at −30 °C and arises from a formal anti-selective carbozincation reaction. Upon warming, the zinc carbenoid is stereochemically labile and isomerizes to its more stable form.

Published
2013

18. Three-carbon homologation of diorganozincs with lithiated acetylenic epoxides

Author

Malika Kaci, Franck Ferreira, Alejandro Perez-Luna, Laurent Debien, Fabrice Chemla, Mathieu Cyklinsky, and Aurelien Denichoux

Subjects
chemistry.chemical_classification, Hydrolysis, Quenching (fluorescence), chemistry, Silylation, Organic Chemistry, chemistry.chemical_element, Organic chemistry, Stereoselectivity, Carbon, Alkyl
Abstract

Reaction of dialkylzincs with lithiated acetylenic epoxides is described to give zincates that undergo a 1,2-metallate rearrangement by an anti-S(N)2' pathway. This rearrangement occurs with the transfer of an alkyl or a silyl group affording allenylzinc intermediates. Allenic and/or homopropargylic alcohols are obtained upon hydrolysis. Quenching the reaction mixture with aldehydes or ketones is shown to give access to 2-alkynyl-1,3-diols in a stereoselective manner.

Published
2012

19. High-yielding synthesis of sphingoid-type bases

Author

Fabrice Chemla, Franck Ferreira, Alejandro Perez-Luna, Candice Botuha, and Catherine Séguin

Subjects
Organic Chemistry, Imine, Sulfonium Compounds, Stereoisomerism, Antineoplastic Agents, Alkenes, Metathesis, Chemical synthesis, Amino Alcohols, Hydrolysis, chemistry.chemical_compound, Zinc, Enantiopure drug, chemistry, Models, Chemical, Sphingosine, Alcohols, Organometallic Compounds, Organic chemistry, Stereoselectivity, Imines
Abstract

An efficient methodology for the synthesis of sphingoid-type bases is reported. It involves the stereoselective addition of a racemic 3-alkoxy allenylzinc to enantiopure N-tert-butylsulfinyl imines and a cross-metathesis reaction as the key steps. It has been successfully applied to the syntheses of sphinganine and naturally occurring bioactive related compounds, among which the hydrolysis product of clavaminol H and two spisulosines. All of these compounds have been prepared in six steps from N-tert-butylsulfinyl imines in high overall yields (>56%).

Published
2009

20. Expeditious synthesis of a common intermediate of L-1-deoxyallonojirimycin and L-1-deoxymannojirimycin

Author

Franck Ferreira, Candice Botuha, Alejandro Perez-Luna, and Fabrice Chemla

Subjects
1-Deoxynojirimycin, Stereochemistry, Organic Chemistry, Imine, L-1-deoxyallonojirimycin, Molecular Conformation, Sulfoxide, Stereoisomerism, L-1-deoxymannojirimycin, Metathesis, Chemical synthesis, Allylamine, chemistry.chemical_compound, chemistry, Cyclization, Yield (chemistry)
Abstract

The expeditious synthesis of a common intermediate of L-1-deoxyallonojirimycin (L-allo-DNJ) and L-1-deoxymannojirimycin (L-manno-DNJ) is reported. This intermediate is obtained in highly diastereo- and enantioselectivity with 38.4% overall yield in six steps involving the unprecedented ring-closing metathesis of a tert-butylsulfinyl allylamine as the key step.

Published
2009

21. Diastereocontrolled synthesis of enantioenriched 3,4-disubstituted beta-prolines

Author

Fabrice Denes, Fabrice Chemla, and and Alejandro Perez-Luna

Subjects
Addition reaction, Proline, Chemistry, Stereochemistry, Organic Chemistry, Molecular Conformation, Stereoisomerism, Chemical synthesis, Domino, Molecular conformation, Carbometalation, Cyclization, Michael reaction, Organic chemistry
Abstract

Enantioenriched 3,4-disubstituted beta-prolines have been prepared with a high diastereocontrol through a carbometalation reaction or through a domino Michael addition/carbometalation reaction.

Published
2007

22. Synthesis of 4,5-trans-Substitued Cyclohexanones

Author

Ernst Peter Kundig, Alejandro Perez-Luna, and Manisankar Sau

Subjects
[Cr(arene)(CO)3] complexes, Stereochemistry, Chemistry, Organic Chemistry, General Medicine, Anisole, C-C bond formation, chemistry.chemical_compound, Dearomatization, ddc:540, Cyclohexenones, Organic chemistry, Nucleophilic/electrophilic addition, Sequence (medicine)
Abstract

Dearomatization of anisole chromiumtricarbonyl by sequential regio- and diastereoselective addition of a C-nucleophile and a C-electrophile is problematic because of competitive ortho-deprotonation. A solution is offered by carrying out the reaction ­sequence with the bis ortho silylated complex. Decomplexation and acid work-up affords 4,5-trans-disubstituted cyclohexenones.

Published
2006

23. Stereoselective Ring Opening of meso Bicyclic Hydrazines: A Straightforward Approach to Hydrazino Cyclopentenic Cores

Author

Michèle Cesario, Laurent Micouin, Alejandro Perez Luna, and Martine Bonin

Subjects
Substitution reaction, Allylic rearrangement, Bicyclic molecule, Stereochemistry, Chemistry, Organic Chemistry, Chiral ligand, General Medicine, Ring (chemistry), Biochemistry, Adduct, Nucleic acid, Stereoselectivity, Physical and Theoretical Chemistry
Abstract

The diastereoselective synthesis of hydrazinocyclopentenes 6 or 7 can be achieved in a straightforward manner from Diels-Alder adduct 4 using an acid-catalyzed rearrangement or a palladium-catalyzed allylic substitution reaction. In the latter case, enantioenriched compounds with ee values up to 58% can be obtained when an appropriate chiral ligand is used. [reaction: see text]

Published
2004

24. Reversal of Enantioselectivity in the Asymmetric Rhodium- versus Iridium-Catalyzed Hydroboration of Meso Substrates

Author

Henri-Philippe Husson, Laurent Micouin, Alejandro Perez Luna, Martine Bonin, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Synthèse et structure de molécules d'interet pharmacologique (SSMIP), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), and Université Pierre et Marie Curie - Paris 6 (UPMC)-ESPCI ParisTech-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS Paris)-Université Pierre et Marie Curie - Paris 6 (UPMC)-ESPCI ParisTech-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS Paris)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Reaction mechanism, Bicyclic molecule, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, chemistry.chemical_element, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Biochemistry, Desymmetrization, Catalysis, 0104 chemical sciences, Rhodium, Hydroboration, Colloid and Surface Chemistry, chemistry, Organic chemistry, Iridium, Enantiomer
Abstract

International audience; The Ir-catalyzed asymmetric hydroboration of bicyclic hydrazines with ee and chemical yields up to 64% is reported. The switch from rhodium to iridium leads systematically to opposite enantiomers in this desymmetrization reaction.

Published
2002

26. Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs

Author

Fabrice Chemla, Florian Dulong, Franck Ferreira, and Alejandro Pérez-Luna

Subjects
carbenoids, carbometallation, carbozincation, radicals, tandem reaction, Science, Organic chemistry, QD241-441
Abstract

The formation of alkylidenezinc carbenoids by 1,4-addition/carbozincation of dialkylzincs or alkyl iodides based on zinc atom radical transfer, in the presence of dimethylzinc with β-(propargyloxy)enoates having pendant iodo- and bromoalkynes, is disclosed. Formation of the carbenoid intermediate is fully stereoselective at −30 °C and arises from a formal anti-selective carbozincation reaction. Upon warming, the zinc carbenoid is stereochemically labile and isomerizes to its more stable form.

Published
2013
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