Review
Chemistry, Inorganic & Nuclear
Pep Rojo, Antoni Riera, Xavier Verdaguer
Summary: Since the development of BisP* ligand by Imamoto, P-stereogenic phosphines bearing a bulky tert-butyl group and a smaller alkyl group have shown remarkable performance in various asymmetric processes. Advances in this class of ligands include the introduction of more rigid backbones, the three-hindered quadrant concept, and the substitution of tert-butyl group with adamantyl. The industrial sector has also contributed by reporting successful P-stereogenic Buchwald-type monophosphines for asymmetric coupling reactions. This review focuses on the synthesis and applications of bulky P-stereogenic phosphines developed since the late 1990s, with a special emphasis on ligands successfully applied in asymmetric catalysis.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Chemistry, Organic
Elzbieta Lastawiecka, Slawomir Frynas, K. Michal Pietrusiewicz
Summary: Two synthetic protocols have been developed for the conversion of 1-phenylphosphinan-4-ones to novel P-stereogenic 1-phenylphosphin-2-en-4-ones. These transformations provide convenient access to optically active 1-phenylphosphin-2-en-4-one 1-sulfide and 1-oxide with enantiomeric purities of 96% and 55%, respectively.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Cheng Luan, Chang-Jiang Yang, Lin Liu, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: Transition metal-catalyzed C-P coupling reactions play a significant role in constructing P-stereogenic centers, with the specific stereochemical mechanism depending on the phosphorus starting materials used. Recent developments in asymmetric catalysis have led to efficient kinetic resolution and dynamic kinetic asymmetric C-P coupling of racemic P-stereogenic compounds.
Article
Chemistry, Multidisciplinary
Ying Zhang, Jia Yuan, Guanglong Huang, Hong Yu, Jinpeng Liu, Jian Chen, Sixuan Meng, Jian-Ji Zhong, Li Dang, Guang-Ao Yu, Chi-Ming Che
Summary: Visible-light-induced reactions play an important role in organic synthesis, but efficient photochemical synthesis of enantiomerically pure molecules remains a challenge. This study describes a simple and efficient visible-light-induced reaction for the synthesis of P-chiral heteroaryl phosphine oxides.
Article
Multidisciplinary Sciences
Katherine C. Forbes, Eric N. Jacobsen
Summary: The stereoselective synthesis of molecules bearing stereogenic phosphorus (V) centers is a challenging task in organic chemistry. Existing methods rely on diastereocontrol using chiral auxiliaries, while catalytic, enantioselective methods offer an alternative approach.
Review
Chemistry, Organic
David S. Glueck
Summary: This review summarizes methods used for asymmetric synthesis of P-stereogenic secondary phosphine oxides, including classical resolution, HPLC separation, and dynamic resolution among others.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Organic
Bence Varga, Peter Szemesi, Petra Nagy, Reka Herbay, Tamas Holczbauer, Elemer Fogassy, Gyorgy Keglevich, Peter Bagi
Summary: Secondary phosphine oxides with various aryl and alkyl groups were synthesized in racemic form and optically resolved using TADDOL derivatives. The resolution method showed good scope under optimized conditions, with successful preparation of enantiopure compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Jan-Erik Siewert, Andre Schumann, Christian Hering-Junghans
Summary: In this study, the selective synthesis of different diaryl diphosphanes and diphosphenes in reductive coupling reactions using PEt3 as a catalyst was demonstrated. The results show the wide applicability of this method in the synthesis of phosphorus compounds. Control experiments revealed a potential oxidation product in the catalytic cycle that could be debrominated by Zn dust as a sacrificial reductant.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Organic
Bin Zhang, Xiao-Ming Zhang, Qing-Wei Zhang
Summary: Phosphine oxides and spirocyclic compounds are privileged molecules that are widely used in catalytic transformations as chiral ligands or bifunctional organocatalysts. In this study, a Pd-catalysed cross-coupling reaction was developed to synthesize spirocyclic amino-phosphine oxides with a P-stereogenic center, which could potentially serve as P*(O), N-ligands or organocatalysts.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Chuanyong Wang, Xiaobo Hu, Cheng Xu, Qiangqiang Ge, Qingliang Yang, Jianqi Xiong, Wei-Liang Duan
Summary: A novel nickel-catalyzed enantioselective C(sp(2))-P cross-coupling has been developed for the synthesis of P-stereogenic phosphine oxides. The reaction of racemic secondary phosphine oxides with alkenyl/aryl bromides produces P-stereogenic phosphine oxides with high yields and enantioselectivities. The method shows excellent tolerance towards various functional groups and has been applied for late-stage functionalization and product transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Xihong Wang, Chi Feng, Julong Jiang, Satoshi Maeda, Koji Kubota, Hajime Ito
Summary: This paper reports the synthesis of silicon-stereogenic silylboranes and the generation of silicon-stereogenic silyl nucleophiles with high enantiopurity and configurational stability. The method is applicable to the synthesis of various silicon-substituted boranes and allows for C-Si bond-forming reactions.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Tanja Huber, Noel Angel Espinosa-Jalapa, Jonathan O. Bauer
Summary: This passage discusses a novel class of phosphines, synthesized enantiomerically pure primary aminophosphine sulfides through stereospecific reductive C-N bond cleavage of phosphorus(V) precursors by lithium in liquid ammonia, and investigates their chemoselectivity. The absolute configurations of all P-stereogenic compounds were determined, with their use as synthetic building blocks demonstrated.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Zeng-Hua Wu, An-Qi Cheng, Meng Yuan, Ya-Xuan Zhao, Huai-Lan Yang, Li-Hua Wei, Huai-Yu Wang, Tao Wang, Zunting Zhang, Wei-Liang Duan
Summary: Utilizing the pyridinyl moiety as the coordinating group in cobalt-catalysed asymmetric nucleophilic addition/alkylation of secondary phosphine oxides can lead to the efficient synthesis of tertiary phosphine oxides with high yields and high enantiomeric excess, along with broad functional-group tolerance. Mechanistic studies reveal that (R)-secondary phosphine oxides preferentially interact with the cobalt catalysts to produce P-stereogenic compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
David S. Glueck
Summary: Metal-catalyzed asymmetric synthesis of P-stereogenic phosphines can produce chiral ligands with valuable applications in asymmetric catalysis, without the need for precious metals. This method can be achieved using earth-abundant metals to develop more active catalysts.
Article
Chemistry, Multidisciplinary
Kyzgaldak Ramazanova, Soumyadeep Chakrabortty, Bernd H. Mueller, Peter Loennecke, Johannes G. de Vries, Evamarie Hey-Hawkins
Summary: A convenient synthesis method for enantiopure mixed donor phosphine-phosphite ligands has been developed, incorporating P-stereogenic phosphanorbornane and axially chiral bisnaphthols into one ligand structure. These ligands exhibited excellent selectivity and moderate enantioselectivity in various catalyzed reactions.
Article
Chemistry, Multidisciplinary
Sebastien Lemouzy, Duc Hanh Nguyen, Valentine Camy, Marion Jean, David Gatineau, Laurent Giordano, Jean-Valere Naubron, Nicolas Vanthuyne, Damien Herault, Gerard Buono
CHEMISTRY-A EUROPEAN JOURNAL
(2015)
Article
Chemistry, Organic
Karel Le Jeune, Sabine Chevallier-Michaud, David Gatineau, Laurent Giordano, Alphonse Tenaglia, Herve Clavier
JOURNAL OF ORGANIC CHEMISTRY
(2015)
Article
Chemistry, Organic
David Gatineau, Duc Hanh Nguyen, Damien Herault, Nicolas Vanthuyne, Julien Leclaire, Laurent Giordano, Gerard Buono
JOURNAL OF ORGANIC CHEMISTRY
(2015)
Article
Chemistry, Organic
Alexandre Lumbroso, Vincent Coeffard, David Gatineau, Sebastian Stecko, Isabelle Beaudet, Jean-Paul Quintard, Erwan Le Grognec
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2016)
Article
Chemistry, Multidisciplinary
Sebastien Lemouzy, Duc Hanh Nguyen, David Gatineau, Laurent Giordano, Damien Herault, Gerard Buono
PURE AND APPLIED CHEMISTRY
(2016)
Article
Physics, Atomic, Molecular & Chemical
David Gatineau, Antony Memboeuf, Anne Milet, Richard B. Cole, Heloise Dossmann, Yves Gimbert, Denis Lesage
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY
(2017)
Article
Biochemical Research Methods
Parisa Bayat, David Gatineau, Denis Lesage, Vincent Robert, Alexandre Martinez, Richard B. Cole
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2019)
Article
Biochemical Research Methods
Parisa Bayat, David Gatineau, Denis Lesage, Sina Marhabaie, Alexandre Martinez, Richard B. Cole
JOURNAL OF MASS SPECTROMETRY
(2019)
Article
Chemistry, Physical
Heloise Dossmann, David Gatineau, Herve Clavier, Antony Memboeuf, Denis Lesage, Yves Gimbert
JOURNAL OF PHYSICAL CHEMISTRY A
(2020)
Article
Physics, Atomic, Molecular & Chemical
David Gatineau, Heloise Dossmann, Herve Clavier, Antony Memboeuf, Laszlo Drahos, Yves Gimbert, Denis Lesage
Summary: The study introduces a new experimental approach using BIRD method to evaluate the dissociation energies of [LAu-CO](+) complexes, providing accurate energy measurements. The results demonstrate that this method is a reliable way to assess ligand effects in gold(I) complexes.
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY
(2021)
Article
Chemistry, Medicinal
Remy Fortrie, David Gatineau, Damien Herault, Aurelie Beal, Jean-Valere Naubron, Laurent Giordano, Gerard Buono
Summary: The racemization mechanism of tert-butylphenylphosphido-borane was investigated experimentally and theoretically, revealing the presence of multiple molecular species during the reaction and the significant contribution of a specific reactive route to the overall racemization process. The study suggests that a phosphido-borane-Li (THF)(2) neutral solvate with P-stereogenic center undergoes monomolecular inversion through a Y-shaped transition structure, playing a key role in the racemization process.
Article
Chemistry, Physical
Marie Vayer, Sophie Rodrigues, Solene Miaskiewicz, David Gatineau, Yves Gimbert, Vincent Gandon, Christophe Bour
Summary: This study describes a gallium-catalyzed C-H propargylation of electron-rich arenes using bromoallenes. By using K2CO3 as a base, the side hydroarylation process catalyzed by adventitious protons from the solvent can be bypassed, and the GaCl3/K2CO3 system is found to trigger a wide range of reactions.
Article
Biochemical Research Methods
Parisa Bayat, David Gatineau, Denis Lesage, Alexandre Martinez, Richard B. Cole
Summary: The synthesis of host molecules with defined characteristics for molecular recognition of guest molecules is a key goal of synthetic host-guest chemistry. Evaluating host selectivity and guest affinities through measuring binding energies is crucial, and mass spectrometry offers a unique opportunity to measure gas-phase binding energies. The presented HCD approach for determining critical energies of dissociation of H-G complexes is a relatively straightforward method that requires prior knowledge of the complexes to obtain their critical energies of dissociation.
JOURNAL OF MASS SPECTROMETRY
(2022)
Article
Chemistry, Inorganic & Nuclear
David Gatineau, Denis Lesage, Herve Clavier, Heloise Dossmann, Chen H. Chan, Anne Milet, Antony Memboeuf, Richard B. Cole, Yves Gimbert
DALTON TRANSACTIONS
(2018)
Article
Chemistry, Physical
Alexandre Vasseur, Romain Membrat, David Gatineau, Alphonse Tenaglia, Didier Nuel, Laurent Giordano