Article
Chemistry, Inorganic & Nuclear
Tomoaki Tanase, Kanako Nakamae, Suzui Hayashi, Ayumi Okue, Risa Otaki, Tomoko Nishida, Yasuyuki Ura, Yasutaka Kitagawa, Takayuki Nakajima
Summary: Binuclear Pd(II) and Pt(II) complexes supported by rac-dpmppm were synthesized with isocyanide ligands, leading to the formation of tetranuclear complexes. Optical resolution of rac-dpmppm was achieved, and chiral octapalladium chains were synthesized and characterized, representing the longest enantiopure chiral single-metal-atom chains structurally characterized to date.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Qiu-Hong Huang, Qian-Yi Zhou, Chen Yang, Li Chen, Jin-Pei Cheng, Xin Li
Summary: An efficient desymmetrizing asymmetric ortho-selective mono-bromination of bisphenol phosphine oxides under chiral squaramide catalysis was reported, leading to a variety of chiral products with high yields and enantioselectivities. The reaction could be scaled up for practical use, demonstrating the synthetic utility of the P-stereogenic compounds in asymmetric reactions.
Review
Chemistry, Multidisciplinary
Junyang Liu, Hang Chen, Min Wang, Wangjin He, Jia-Lei Yan
Summary: This article summarizes the key achievements in organocatalytic methodologies for the synthesis of organophosphorus compounds with P-stereogenic centers. Different catalytic systems are highlighted for each strategy class (desymmetrization, kinetic resolution, and dynamic kinetic resolution), and examples are provided to illustrate the potential applications of these P-stereogenic organophosphorus compounds.
FRONTIERS IN CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Chuanyong Wang, Qingliang Yang, Yuan-Hao Dai, Jianqi Xiong, Yu Zheng, Wei-Liang Duan
Summary: This study presents the first nickel-catalyzed synthesis of P-stereogenic secondary aminophosphine-boranes through the asymmetric addition of primary phosphines to azo compounds. The versatility of these synthesized P-stereogenic compounds allows for the facile synthesis of both known and novel P-stereogenic compounds through sequential and stereospecific reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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.
Article
Chemistry, Organic
Tao Zhou, Ling-Jie Fan, Zi-Jia Chen, Meng-Xue Jiang, Pu-Fan Qian, Xinquan Hu, Kun Zhang, Bing-Feng Shi
Summary: In this study, we describe the preparation of various structurally diverse P-stereogenic phosphinamides through Pd(II)-catalyzed enantioselective C-H alkynylation using cheap commercially available l-pyroglutamic acid as a chiral ligand. The reactions showed good yields and high enantioselectivities via desymmetrization and kinetic resolution. The presence of a tailor-made congested directing group, N-ethyl-N-(3-methylpyridin-2-yl)amino, was crucial for the reactivity.
Article
Chemistry, Organic
Ross A. Arthurs, Alice C. Dean, David L. Hughes, Christopher J. Richards
Summary: Starting from (R)-Ugi's amine, diastereoselective lithiation followed by Ar'PCl2 and then Ar''MgBr led to the generation of single diastereoisomers of PPFA ligand derivatives. The derived CuCl complexes showed competent catalyst precursors for enantioselective conjugate addition reactions, avoiding the isolation of air-sensitive phosphine intermediates.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Maria Biosca, Pol de la Cruz-Sanchez, Jorge Faiges, Jessica Margalef, Ernest Salomo, Antoni Riera, Xavier Verdaguer, Joan Ferre, Feliu Maseras, Maria Besora, Oscar Pamies, Montserrat Dieguez
Summary: Ir-MaxPHOX-type catalysts exhibit high catalytic performance in the hydrogenation of a wide range of nonchelating olefins with different geometries, substitution patterns, and degrees of functionalization. These air-stable and readily available catalysts have been successfully used in the asymmetric hydrogenation of di-, tri-, and tetrasubstituted olefins (ee ' s up to 9996). The combination of theoretical calculations and deuterium labeling experiments has revealed the factors responsible for the observed enantioselectivity, allowing for the rationalization of suitable substrates for these Ircatalysts.
Article
Chemistry, Multidisciplinary
Yulong Zhang, Peichao Zhao, Shengnan Sun, Qian Wu, Enxue Shi, Junhua Xiao
Summary: The authors developed a camphor-derived 2,3-diol as a chiral template to synthesize diverse P(III) and P(V) chiral compounds, which are highly desirable for asymmetric catalysis in organic chemistry.
COMMUNICATIONS CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Roman Franz, Clemens Bruhn, Rudolf Pietschnig
Summary: In this study, tert-Butyl-substituted diphospha[2]ferrocenophane was utilized as a stereochemically confined diphosphane to investigate the addition of various dichalcoganes. Bischalcogenophosphinous acid esters with four soft donor sides were obtained and characterized, and the coordination chemistry of multidentate ligand 3b towards d(10) coinage metal centers was explored, resulting in various bimetallic complexes.
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
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, Multidisciplinary
Yanli Li, Xiao Jin, Peng Liu, Haijuan Zhang, Xiuling Yu, Yanjuan Liu, Baixue Liu, Wenqiang Yang
Summary: A copper-catalyzed asymmetric aryl C-P cross-coupling/cyclization reaction was developed via dynamic kinetic asymmetric transformation, providing a general and simple method for enantioselective synthesis of stable P-stereogenic phosphorus heterocycles with excellent enantioselectivities and moderate to high yields. Gram-scale asymmetric synthesis of P-stereogenic P-heterocycle from commercially available materials was also successfully accomplished with excellent enantioselectivity and high yield.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Javier Eusamio, Yaiza M. Medina, Javier C. Cordoba, Anton Vidal-Ferran, Daniel Sainz, Albert Gutierrez, Merce Font-Bardia, Arnald Grabulosa
Summary: Enantiopure P-stereogenic methylphosphane-boranes have been used to prepare organometallic compounds with chiral phosphine ligands. These compounds exhibit good catalytic activity and selectivity in hydrogenation and transfer hydrogenation reactions.
DALTON TRANSACTIONS
(2023)
Article
Biochemistry & Molecular Biology
Ahmed Numan, Matthew Brichacek
Summary: This study successfully synthesized chiral phosphonate products using chiral nucleophilic catalysis, providing new possibilities for transition metal catalysis and nucleotide therapeutics.
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, Multidisciplinary
Ryan M. Tipker, Jake A. Muldoon, Daniel H. Pham, Balazs R. Varga, Russell P. Hughes, David S. Glueck, Gary J. Balaich, Arnold L. Rheingold
Summary: Tetrahedral main-group compounds are configurationally stable, but chiral phosphiranium cations can undergo P-epimerization under mild conditions. Ion exchange and chromatography can be used to separate the resulting mixtures of syn- and anti-isomers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Guobi Li, Rhett Smith, Milan Gembicky, Arnold L. Rheingold, John D. Protasiewicz
Summary: In this study, a di-hypervalent iodine compound was synthesized using a bulky 1,4-di-iodobenzene with four para-Bu-t-C6H4 group substituents. The compound underwent cyclization under mild conditions to form a dicyclic di-iodonium di-triflate salt. The introduction of para-tert-butyl groups improved the solubility of the compounds, making them more suitable for applications as recyclable reagents, materials precursors, and Lewis acids.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Zakary T. Ekstrom, Arnold L. Rheingold, John D. Protasiewicz
Summary: Two bis(benzoxaphosphole)s were synthesized and characterized, with one compound exhibiting flexibility in structure and blue fluorescence, while the other compound showed no significant emission due to the quenching ability of ferrocene in its excited state.
PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS
(2022)
Article
Chemistry, Physical
Muyuan Zhao, Jayvic C. Jimenez, Chunlai Wang, Guanchun Rui, Tingrui Ma, Chenwei Lu, Arnold L. Rheingold, Ruipeng Li, Lei Zhu, Genevieve Sauve
Summary: This study explores the fluorination of a zinc(II) complex to increase intermolecular pi-pi stacking interactions and improve electron mobility and organic photovoltaic performance.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Inorganic & Nuclear
Jorge A. Garduno, David S. Glueck, Ritchie E. Hernandez, Joshua S. Figueroa, Arnold L. Rheingold
Summary: In this study, it was discovered through a series of experiments that under specific conditions, the weakly coordinating fluorinated tetraarylborate anion can react with a platinum cation and weak acid water at room temperature, decomposing three bonds and producing new compounds.
Article
Chemistry, Physical
Thomas Louis-Goff, Huu Vinh Trinh, Eileen Chen, Arnold L. Rheingold, Christian Ehm, Jakub Hyvl
Summary: An efficient catalytic difluorocarbenation reaction has been developed to synthesize 1,1-difluorocyclopropanes using an organobismuth complex as the catalyst and TMS-CF3 as the difluorocarbene source. The reaction exhibits wide substrate scope and good robustness, generating the desired products with high selectivity. The mechanism of difluorocarbene generation and the high selectivity have been studied through experiments and theoretical calculations.
Article
Chemistry, Inorganic & Nuclear
Sarah K. Gallant, Ryan M. Tipker, David S. Glueck
Summary: The development of metal-catalyzed asymmetric synthesis of phosphines has been guided by the hypothesis that rapid pyramidal inversion occurs in metal-phosphido intermediates. In this study, we observed the formation of reaction intermediates and found low-barrier pyramidal inversion at phosphorus in the key P-stereogenic terminal phosphido complexes. Additionally, we investigated the reversible formation of these complexes from secondary phosphine-silanolate complexes.
Article
Chemistry, Multidisciplinary
Sloane Evariste, Alexandra M. Harrison, Sunandan Sarkar, Arnold L. Rheingold, Barry D. Dunietz, Joachim W. Heinicke, Emalyn Delgado Rosario, Sungwoon Yoon, Thomas S. Teets, John D. Protasiewicz
Summary: 2-R-1H-1,3-Benzazaphospholes are an interesting class of heterocycles with P=C bonds. This study presents the synthesis and structural characterization of a new R-BAP (R = 2,2'-dithiophene) and compares its photoluminescence with two previously reported R-BAPs (R,R' = Me and R = 2-thiophene). The thiophene derivatives exhibit significant fluorescence, while the methyl-substituted analogue shows weak emission.
Article
Chemistry, Inorganic & Nuclear
Lihua Liu, Daniel Mendoza-Espinosa, Mauricio Quiroz-Guzman, Arnold L. Rheingold, Tracy A. Hanna, Gobinda Saha, Liming Tang, Yanhui Chen, Megan Gilbert, Abhirup Dutta, Alexandru D. Asandei
Summary: A series of methylene-bridged bisphenol ligands were synthesized and reacted with TiCl4, CpTiCl3, or Ti(OiPr)4 to form corresponding complexes, which were characterized and found to exhibit good reactivity in polymerization reactions.
Article
Chemistry, Inorganic & Nuclear
Sarah T. Chachula, Perry M. Scheetz, Andrew H. Zureick, Russell P. Hughes, David S. Glueck, Ritchie E. Hernandez, Joshua S. Figueroa, Arnold L. Rheingold
Summary: Catalytic asymmetric dehydrocoupling of secondary phosphines can produce enantiomerically enriched P-stereogenic diphosphines for the synthesis of chiral ligands or building blocks. Rh(diphos*) catalyst precursors converted a rac/meso mixture of PhP(CH2)(3)PPh(1) to a C-2-symmetric P-stereogenic anti-diphospholane PhP(CH2)(3)PPh (2) with an enantiomeric ratio (er) of up to 58:42 and complete diastereoselectivity via catalyst-mediated isomerization. NMR studies revealed the resting state Rh((R,R)-i-Pr-DuPhos) PhP(CH2)(3)PPh (4) and proposed a mechanism involving oxidative addition and reductive elimination steps for stereocontrolled P-P bond formation.
Article
Chemistry, Inorganic & Nuclear
Preston M. Miura-Akagi, Timothy W. Chapp, Wesley Y. Yoshida, Glenn P. A. Yap, Arnold L. Rheingold, Russell P. Hughes, Matthew F. Cain
Summary: Dearomatization of N-Dipp-substituted benzazaphosphole 2 with HCl produced 1-Cl, which could be further substituted by halide sources to obtain the other members of the P halogenated series. Characterization of these P-heterocycles (1) was performed using multinuclear NMR spectroscopy, elemental analysis, and X-ray crystallography. The study also explored the reaction of 1-Br/I with [Pt(P(t-Bu)3)2], resulting in the formation of Pt(I)-Pt(I) dimers 4-Br/I, and the addition of 1-F to Pt(PPh3)4, leading to the coordination compound Pt(1-F)(PPh3)2.
Article
Chemistry, Multidisciplinary
Ryan M. Tipker, Jake A. Muldoon, Jacob Jo, Christopher S. Connors, Balazs R. Varga, Russell P. Hughes, David S. Glueck
Summary: Protonation of phosphiranes with triflic acid resulted in ring opening and cyclophosphination, leading to the formation of phospholanium cations. This study discovered a new reactivity pattern for phosphiranes.
Article
Biochemistry & Molecular Biology
Mariola Flores-Rivera, Jose Carmona-Negron, Arnold Rheingold, Enrique Melendez
Summary: 3-ferrocenyl-estra-1,3,5(10)-triene-17-one (2), [Fe(C5H5)(C24H25O3)], crystallizes in monoclinic space group C2. The Cp rings adopt a nearly eclipsed conformation, and the Cp plane is tilted with respect to the substituted phenyl plane. Weak intermolecular interactions such as C-H···π and C-H···O were analyzed. Density functional theory studies revealed a rotational barrier for the C3-O1 bond. Fluorescence quenching and in silico docking studies suggest that human serum albumin forms a complex via van der Waals and hydrogen bonding interactions.
