Synthetische Chemie (Baudoin)Head of Research Unit Prof. Dr.Olivier BaudoinOverviewMembersPublicationsProjects & CollaborationsProjects & Collaborations OverviewMembersPublicationsProjects & Collaborations Projects & Collaborations 6 foundShow per page10 10 20 50 Development of Ni-catalyzed C-H arylation reactions Research Project | 1 Project MembersImported from Grants Tool 4708324 Addressing challenging amination reactions with metal nitrenes Research Project | 1 Project MembersImported from Grants Tool 4699638 Synthesis of aminoalcohols by C(sp3)-H activation Research Project | 1 Project MembersNo Description available Development of challenging Pd0-catalyzed enantioselective C(sp3)-H activation reactions Research Project | 1 Project MembersThis proposal focuses on the development of challenging enantioselective C-H activation reactions that proceed by palladium(0)-catalysis. It builds on previous research from our group in this field and on the analysis of current gaps and challenges. The proposal is divided into four independent Work Packages (WP), wherein different types of chiral catalysts will be employed. WP1 is dedicated to the development of an enantioselective method to synthesize axially chiral spirocycles, involving a double C(sp3)-H arylation and the desymmetrization of enantiotopic methyl groups in the enantiodetermining step. This method should provide a straightforward access to original spirocyclic molecules wherein the stereogenic axis is the sole stereogenic element. In WP2, we will investigate the yet unexplored kinetic resolution of racemic reactants by Pd0-catalyzed activation of sp2 and sp3 C-H bonds in the presence of a chiral catalyst. Ideally, both enantiomers of the corresponding cyclic products could be formed by reacting the remaining enantiomer in the presence of an achiral catalyst. Applications to the synthesis of polycyclic natural products are envisaged for selected cases. The main purpose of WP3, for which we already have very significant preliminary results, is the Pd0-catalyzed functionalization of enantiotopic secondary C-H bonds. These are less reactive than primary ones and more challenging to activate, but lead to the creation of a stereocenter at the activated site and have a great application potential. The use of C2-symmetric N-heterocyclic carbenes of the IBiox family should allow achieving high enantioselectivities for a range of synthetically appealing carbo- and heterocyclic products. The developed methods will be applied to the synthesis of selected natural products such as indidene C. WP4 is dedicated to the development of the intermolecular enantioselective C-H functionalization of enantiotopic secondary C-H bonds. The use of palladium(0) instead of the more established palladium(II) catalysis would enable cross-couplings with a variety of compatible electrophiles. Reactions of substrates bearing simple monodentate directing groups, potentially leading to a range of valuable enantioenriched carboxylic acid, amine or alcohol building blocks in a straightforward manner, will be investigated. C-H Bond Functionalization via Catalytic Migrative Cross-Coupling Research Project | 1 Project MembersThis proposal is dedicated to the development of a new C-H functionalization strategy allowing to selectively create a C-C bond at the terminal position of an alkane fragment. This strategy is based on the ability of group 10 metals to migrate along an alkyl chain via the ß-H elimination/p-complex rotation/insertion mechanism and undergo reductive elimination at the least substituted terminal position. This proposal features 3 Work Packages (WP) of progressively more challenging character. In WP1, the palladium(0)-catalyzed ligand-controlled regioconvergent coupling of organozinc compounds, obtained from mixtures of alkyl bromides, is proposed. Coupling this migrative cross-coupling with an initial C-H bromination step would allow to selectively functionalize alkanes in two-steps at the terminal carbon. WP2 features the development of a nickel-catalyzed version of the preceding migrative coupling, which would offer a useful complementarity both in terms of scope and mechanism. The main purpose of WP3 is to replace organozinc reagents employed in the Ni-catalyzed process (WP2) with photoredox-generated radicals, such as those generated from carboxylic acids or amines in combination with an Ir-based photocatalyst. This modification would allow to significantly expand the scope and practicability of this C-H functionalization strategy. CHIBACHA - Chiral Base C-H Activation Research Project | 1 Project MembersThe goal of this proposal is to develop a new strategy for asymmetric C(sp3)−H activation using a chiral base instead of chiral ligand, and will focus on oxidative addition-induced and decarboxylation-induced reactions. Using this new strategy, a wide range of representative and valuable chiral four-membered (hetero)cyclic and five-membered (hetero)cyclic organic molecules will be synthesized. Typical chiral Br¢nsted acids and the designed ionic liquid-functionalized chiral phosphoric acids will be prepared by using commercially available raw materials. They will be tested in the two proposed concepts. In the case of oxidative addition-induced reactions, some feasible examples aiming at synthesizing chiral indanes, indolines, dihydrobenzofurans, benzocyclobutenes, and lactams will be developed from readily available aryl or alkenyl halides or triflates. For the decarboxylation-induced reactions, a racemic version will be first developed. Then, the chiral base concept will be applied in the synthesis of chiral benzocyclobutenes, indanes, indolines, and dihydrobenzofurans. In each of the reactions involved, some key reaction parameters including chiral acid, ligand, solvent, base, reaction temperature as well as the structural features of the substrates will be studied. In addition, recyclable ionic liquid-functionalized chiral Br¢nsted acids and the effect of traditional ionic liquids as the additives or solvents will be first studied in enantioselective C(sp3)−H bond activation. In order to get a clear understanding on the nature of the asymmetric induction during the catalytic cycle, computational studies will also be performed using DFT methods. The applicant's previous research experience in C−H activation, ionic liquids catalysis and asymmetric catalysis areas will benefit the project. The project will foster mutually beneficial research collaboration in Europe in the field of C−H activation and green chemistry. 1 1 OverviewMembersPublicationsProjects & Collaborations
Projects & Collaborations 6 foundShow per page10 10 20 50 Development of Ni-catalyzed C-H arylation reactions Research Project | 1 Project MembersImported from Grants Tool 4708324 Addressing challenging amination reactions with metal nitrenes Research Project | 1 Project MembersImported from Grants Tool 4699638 Synthesis of aminoalcohols by C(sp3)-H activation Research Project | 1 Project MembersNo Description available Development of challenging Pd0-catalyzed enantioselective C(sp3)-H activation reactions Research Project | 1 Project MembersThis proposal focuses on the development of challenging enantioselective C-H activation reactions that proceed by palladium(0)-catalysis. It builds on previous research from our group in this field and on the analysis of current gaps and challenges. The proposal is divided into four independent Work Packages (WP), wherein different types of chiral catalysts will be employed. WP1 is dedicated to the development of an enantioselective method to synthesize axially chiral spirocycles, involving a double C(sp3)-H arylation and the desymmetrization of enantiotopic methyl groups in the enantiodetermining step. This method should provide a straightforward access to original spirocyclic molecules wherein the stereogenic axis is the sole stereogenic element. In WP2, we will investigate the yet unexplored kinetic resolution of racemic reactants by Pd0-catalyzed activation of sp2 and sp3 C-H bonds in the presence of a chiral catalyst. Ideally, both enantiomers of the corresponding cyclic products could be formed by reacting the remaining enantiomer in the presence of an achiral catalyst. Applications to the synthesis of polycyclic natural products are envisaged for selected cases. The main purpose of WP3, for which we already have very significant preliminary results, is the Pd0-catalyzed functionalization of enantiotopic secondary C-H bonds. These are less reactive than primary ones and more challenging to activate, but lead to the creation of a stereocenter at the activated site and have a great application potential. The use of C2-symmetric N-heterocyclic carbenes of the IBiox family should allow achieving high enantioselectivities for a range of synthetically appealing carbo- and heterocyclic products. The developed methods will be applied to the synthesis of selected natural products such as indidene C. WP4 is dedicated to the development of the intermolecular enantioselective C-H functionalization of enantiotopic secondary C-H bonds. The use of palladium(0) instead of the more established palladium(II) catalysis would enable cross-couplings with a variety of compatible electrophiles. Reactions of substrates bearing simple monodentate directing groups, potentially leading to a range of valuable enantioenriched carboxylic acid, amine or alcohol building blocks in a straightforward manner, will be investigated. C-H Bond Functionalization via Catalytic Migrative Cross-Coupling Research Project | 1 Project MembersThis proposal is dedicated to the development of a new C-H functionalization strategy allowing to selectively create a C-C bond at the terminal position of an alkane fragment. This strategy is based on the ability of group 10 metals to migrate along an alkyl chain via the ß-H elimination/p-complex rotation/insertion mechanism and undergo reductive elimination at the least substituted terminal position. This proposal features 3 Work Packages (WP) of progressively more challenging character. In WP1, the palladium(0)-catalyzed ligand-controlled regioconvergent coupling of organozinc compounds, obtained from mixtures of alkyl bromides, is proposed. Coupling this migrative cross-coupling with an initial C-H bromination step would allow to selectively functionalize alkanes in two-steps at the terminal carbon. WP2 features the development of a nickel-catalyzed version of the preceding migrative coupling, which would offer a useful complementarity both in terms of scope and mechanism. The main purpose of WP3 is to replace organozinc reagents employed in the Ni-catalyzed process (WP2) with photoredox-generated radicals, such as those generated from carboxylic acids or amines in combination with an Ir-based photocatalyst. This modification would allow to significantly expand the scope and practicability of this C-H functionalization strategy. CHIBACHA - Chiral Base C-H Activation Research Project | 1 Project MembersThe goal of this proposal is to develop a new strategy for asymmetric C(sp3)−H activation using a chiral base instead of chiral ligand, and will focus on oxidative addition-induced and decarboxylation-induced reactions. Using this new strategy, a wide range of representative and valuable chiral four-membered (hetero)cyclic and five-membered (hetero)cyclic organic molecules will be synthesized. Typical chiral Br¢nsted acids and the designed ionic liquid-functionalized chiral phosphoric acids will be prepared by using commercially available raw materials. They will be tested in the two proposed concepts. In the case of oxidative addition-induced reactions, some feasible examples aiming at synthesizing chiral indanes, indolines, dihydrobenzofurans, benzocyclobutenes, and lactams will be developed from readily available aryl or alkenyl halides or triflates. For the decarboxylation-induced reactions, a racemic version will be first developed. Then, the chiral base concept will be applied in the synthesis of chiral benzocyclobutenes, indanes, indolines, and dihydrobenzofurans. In each of the reactions involved, some key reaction parameters including chiral acid, ligand, solvent, base, reaction temperature as well as the structural features of the substrates will be studied. In addition, recyclable ionic liquid-functionalized chiral Br¢nsted acids and the effect of traditional ionic liquids as the additives or solvents will be first studied in enantioselective C(sp3)−H bond activation. In order to get a clear understanding on the nature of the asymmetric induction during the catalytic cycle, computational studies will also be performed using DFT methods. The applicant's previous research experience in C−H activation, ionic liquids catalysis and asymmetric catalysis areas will benefit the project. The project will foster mutually beneficial research collaboration in Europe in the field of C−H activation and green chemistry. 1 1
Development of Ni-catalyzed C-H arylation reactions Research Project | 1 Project MembersImported from Grants Tool 4708324
Addressing challenging amination reactions with metal nitrenes Research Project | 1 Project MembersImported from Grants Tool 4699638
Synthesis of aminoalcohols by C(sp3)-H activation Research Project | 1 Project MembersNo Description available
Development of challenging Pd0-catalyzed enantioselective C(sp3)-H activation reactions Research Project | 1 Project MembersThis proposal focuses on the development of challenging enantioselective C-H activation reactions that proceed by palladium(0)-catalysis. It builds on previous research from our group in this field and on the analysis of current gaps and challenges. The proposal is divided into four independent Work Packages (WP), wherein different types of chiral catalysts will be employed. WP1 is dedicated to the development of an enantioselective method to synthesize axially chiral spirocycles, involving a double C(sp3)-H arylation and the desymmetrization of enantiotopic methyl groups in the enantiodetermining step. This method should provide a straightforward access to original spirocyclic molecules wherein the stereogenic axis is the sole stereogenic element. In WP2, we will investigate the yet unexplored kinetic resolution of racemic reactants by Pd0-catalyzed activation of sp2 and sp3 C-H bonds in the presence of a chiral catalyst. Ideally, both enantiomers of the corresponding cyclic products could be formed by reacting the remaining enantiomer in the presence of an achiral catalyst. Applications to the synthesis of polycyclic natural products are envisaged for selected cases. The main purpose of WP3, for which we already have very significant preliminary results, is the Pd0-catalyzed functionalization of enantiotopic secondary C-H bonds. These are less reactive than primary ones and more challenging to activate, but lead to the creation of a stereocenter at the activated site and have a great application potential. The use of C2-symmetric N-heterocyclic carbenes of the IBiox family should allow achieving high enantioselectivities for a range of synthetically appealing carbo- and heterocyclic products. The developed methods will be applied to the synthesis of selected natural products such as indidene C. WP4 is dedicated to the development of the intermolecular enantioselective C-H functionalization of enantiotopic secondary C-H bonds. The use of palladium(0) instead of the more established palladium(II) catalysis would enable cross-couplings with a variety of compatible electrophiles. Reactions of substrates bearing simple monodentate directing groups, potentially leading to a range of valuable enantioenriched carboxylic acid, amine or alcohol building blocks in a straightforward manner, will be investigated.
C-H Bond Functionalization via Catalytic Migrative Cross-Coupling Research Project | 1 Project MembersThis proposal is dedicated to the development of a new C-H functionalization strategy allowing to selectively create a C-C bond at the terminal position of an alkane fragment. This strategy is based on the ability of group 10 metals to migrate along an alkyl chain via the ß-H elimination/p-complex rotation/insertion mechanism and undergo reductive elimination at the least substituted terminal position. This proposal features 3 Work Packages (WP) of progressively more challenging character. In WP1, the palladium(0)-catalyzed ligand-controlled regioconvergent coupling of organozinc compounds, obtained from mixtures of alkyl bromides, is proposed. Coupling this migrative cross-coupling with an initial C-H bromination step would allow to selectively functionalize alkanes in two-steps at the terminal carbon. WP2 features the development of a nickel-catalyzed version of the preceding migrative coupling, which would offer a useful complementarity both in terms of scope and mechanism. The main purpose of WP3 is to replace organozinc reagents employed in the Ni-catalyzed process (WP2) with photoredox-generated radicals, such as those generated from carboxylic acids or amines in combination with an Ir-based photocatalyst. This modification would allow to significantly expand the scope and practicability of this C-H functionalization strategy.
CHIBACHA - Chiral Base C-H Activation Research Project | 1 Project MembersThe goal of this proposal is to develop a new strategy for asymmetric C(sp3)−H activation using a chiral base instead of chiral ligand, and will focus on oxidative addition-induced and decarboxylation-induced reactions. Using this new strategy, a wide range of representative and valuable chiral four-membered (hetero)cyclic and five-membered (hetero)cyclic organic molecules will be synthesized. Typical chiral Br¢nsted acids and the designed ionic liquid-functionalized chiral phosphoric acids will be prepared by using commercially available raw materials. They will be tested in the two proposed concepts. In the case of oxidative addition-induced reactions, some feasible examples aiming at synthesizing chiral indanes, indolines, dihydrobenzofurans, benzocyclobutenes, and lactams will be developed from readily available aryl or alkenyl halides or triflates. For the decarboxylation-induced reactions, a racemic version will be first developed. Then, the chiral base concept will be applied in the synthesis of chiral benzocyclobutenes, indanes, indolines, and dihydrobenzofurans. In each of the reactions involved, some key reaction parameters including chiral acid, ligand, solvent, base, reaction temperature as well as the structural features of the substrates will be studied. In addition, recyclable ionic liquid-functionalized chiral Br¢nsted acids and the effect of traditional ionic liquids as the additives or solvents will be first studied in enantioselective C(sp3)−H bond activation. In order to get a clear understanding on the nature of the asymmetric induction during the catalytic cycle, computational studies will also be performed using DFT methods. The applicant's previous research experience in C−H activation, ionic liquids catalysis and asymmetric catalysis areas will benefit the project. The project will foster mutually beneficial research collaboration in Europe in the field of C−H activation and green chemistry.
