Article
Multidisciplinary Sciences
Lara E. Zetzsche, Jessica A. Yazarians, Suman Chakrabarty, Meagan E. Hinze, Lauren A. M. Murray, April L. Lukowski, Leo A. Joyce, Alison R. H. Narayan
Summary: This study demonstrates the use of cytochrome P450 enzymes for biocatalytic cross-coupling reactions, enabling the formation of sterically hindered biaryl bonds through oxidative C-C bond formation. By engineering the substrate and atroposelectivity of the P450 enzyme, a highly efficient and selective process has been developed.
Article
Chemistry, Physical
Paul O. Peterson, Matthew Joannou, Eric M. Simmons, Steven R. Wisniewski, Junho Kim, Paul J. Chirik
Summary: The synthesis and characterization of phenoxy(imine) iron(II) alkyl precatalysts for C(sp2)-C(sp3) Suzuki-Miyaura cross-coupling reaction is reported. This method utilizes mild alkoxide bases and nonpolar solvents to achieve high efficiency C(sp2)-C(sp3) bond formation with various aryl boronic esters and alkyl bromides. The study also highlights the compatibility of the precatalysts with base-sensitive functionality and the role of boronate intermediates in transmetalation.
Article
Chemistry, Organic
Wen-Xin Li, Bo-Wen Yang, Xuan Ying, Zhuo-Wen Zhang, Xue-Qiang Chu, Xiaocong Zhou, Mengtao Ma, Zhi-Liang Shen
Summary: The direct cross-coupling of diaryl sulfoxides with aryl bromides via C-S bond cleavage was achieved using nickel(II) as the catalyst, 1,2-bis(diphenylphosphino)ethane (dppe) as the ligand, and magnesium turnings as the reducing metal in THF. This reaction showed a wide range of substrates and could be used for gram-scale synthesis. The one-pot reaction is operationally simple and economically efficient.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Antonio J. LaPorte, Yao Shi, Jason E. Hein, Martin D. Burke
Summary: Stereospecific Csp(3) Suzuki-Miyaura cross-coupling simplifies the synthesis of stereochemically complex small molecules, but current methods are not compatible with complex building blocks commonly found in natural products and other complex targets. This study presents a method for embedding the alpha-methyl-beta-hydroxyl motif within stereochemically defined secondary alkyl boronic ester building blocks, allowing for stereospecific cross-coupling. The use of beta-aryloxysilyl groups addresses the decrease in reactivity and side reactions associated with beta-oxygen-containing Csp(3) boronic esters. Mechanistic studies reveal the activation of a dihydroxysiloxaborolate as a transmetalation partner in a stereospecific process that retains configuration.
Article
Chemistry, Organic
Feiyan Yang, Chuan Wang
Summary: In this study, we employ polycyclic aryl-activated alkyl ammonium triflates as the electrophilic aryl-activated alkylating agent in the nickel-catalyzed hydroxyl- or sulfonamide-directed cross-electrophile coupling reaction with phenyl benzoates, resulting in the synthesis of diverse aryl ketones under mild conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Jacob R. Ludwig, Eric M. Simmons, Steven R. Wisniewski, Paul J. Chirik
Summary: A cobalt-catalyzed method for the C(sp(2))-C(sp(3)) Suzuki-Miyaura cross coupling of aryl boronic esters and alkyl bromides was developed, with cobalt-ligand combinations being assessed through high-throughput experimentation. The use of cobalt(II) sources with trans-N,N'-dimethylcyclohexane-1,2-diamine (DMCyDA, L-1) resulted in optimal yield and selectivity. The transformation allowed for diverse steric and electronic properties on the aryl boronate nucleophile as well as various levels of branching and synthetically valuable functionality on the electrophile, with radical trap experiments supporting the formation of electrophile-derived radicals during catalysis.
Article
Chemistry, Organic
John E. A. Russell, Sharon R. Neufeldt
Summary: The chemoselective cross-coupling of phenol derivatives is valuable for synthesizing products with retained halides. This review focuses on recent developments in selective cross-couplings of chloroaryl phenol derivatives, particularly reactions involving chloroaryl tosylates. A detailed discussion is provided on the first example of a C-O-selective Ni-catalyzed Suzuki-Miyaura coupling of chloroaryl tosylates.
Article
Chemistry, Physical
L. Reginald Mills, David Gygi, Jacob R. Ludwig, Eric M. Simmons, Steven R. Wisniewski, Junho Kim, Paul J. Chirik
Summary: In this study, efficient precatalysts for the C(sp(2))-C(sp(3)) Suzuki-Miyaura cross-coupling reaction between alkyl bromides and neopentylglycol (hetero)arylboronic esters were generated in situ using Cobalt(II) halides in combination with phenoxyimine (FI) ligands. The protocol allowed for efficient C-C bond formation with various nucleophiles and electrophiles. The results also suggested that alkyl radicals play an important role in the catalytic reaction.
Review
Chemistry, Physical
Brijesh S. Kadu
Summary: Palladium has been widely used in the Suzuki-Miyaura cross coupling reaction for over 30 years, but it comes with drawbacks such as high cost, tedious work-ups, product contamination, and metal leaching. In recent years, other metals like Ni, Cu, Co, Fe, Rh, and Ru have attracted attention for their potential in SMCR, allowing for the synthesis of industrially important compounds with various functional groups. This review discusses recent advancements in catalysis related to SMCR, providing valuable insights for researchers in designing synthetic protocols for pharmacophores and drug molecules.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Applied
Mingyang Gao, Jiamin Wang, Weixiang Shang, Yuchao Chai, Weili Dai, Guangjun Wu, Naijia Guan, Landong Li
Summary: Suzuki-Miyaura cross-coupling reaction is a powerful method to construct carbon-carbon bonds and is widely used in the synthesis of functional organic compounds. In this study, zeolite-encased Pd particles (Pd@MFI) were successfully prepared and investigated as promising heterogeneous catalysts for the Suzuki-Miyaura cross-coupling reaction. The Pd@MFI catalysts showed high activity, with dispersed Pd particles efficiently stabilized within the MFI zeolite matrix. The presence of basic sites adjacent to Pd sites was crucial for achieving high catalytic activity.
Article
Multidisciplinary Sciences
Kai Yang, Yanfei Mao, Zhihan Zhang, Jie Xu, Hao Wang, Yong He, Peiyuan Yu, Qiuling Song
Summary: The authors report a tetracoordinate boron-directed dynamic kinetic asymmetric transformation (DyKAT) method for the construction of C-B axial chirality using racemic, configurationally stable 3-bromo-2,1-azaborines. By rational design of a reversible tetracoordinate boron intermediate, a series of challenging C-B axially chiral compounds were prepared with generally good to excellent enantioselectivities. This method can also be extended to prepare atropisomers bearing adjacent C-B and C-C diaxes with excellent diastereo- and enantio-control.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Jie Xu, Samantha Grosslight, Kyle A. Mack, Sierra C. Nguyen, Kyle Clagg, Ngiap-Kie Lim, Jacob C. Timmerman, Jeff Shen, Nicholas A. White, Lauren E. Sirois, Chong Han, Haiming Zhang, Matthew S. Sigman, Francis Gosselin
Summary: An efficient asymmetric synthesis of a potent KRAS G12C covalent inhibitor, GDC-6036, was reported. The synthesis involved a highly selective Negishi coupling and a series of reaction sequences, leading to the desired compound with a 40% overall yield from the starting materials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Biochemistry & Molecular Biology
Martina Hurtova, David Biedermann, Zuzana Osifova, Josef Cvacka, Katerina Valentova, Vladimir Kren
Summary: In this study, we utilized the Suzuki-Miyaura cross-coupling reaction to synthesize a library of flavonoid derivatives for biological activity assays. We explored the reactivity of halogenated flavonoids with aryl boronates and boronyl flavonoids. This method enabled the preparation of various flavonoid derivatives substituted at C-8, and was successfully applied to the synthesis of natural compounds and rare C-8 hydroxyflavonoids.
Article
Chemistry, Organic
Masato Tsuda, Taiki Morita, Hiroyuki Nakamura
Summary: The Suzuki-Miyaura cross-coupling of 3,4-disubstituted 5-bromoisoxazoles at the C5 position using Pd-2(dba)(3) and P(t-Bu)(3)center dot HBF4 catalysts successfully yielded trisubstituted isoxazoles while suppressing the formation of ketone 4 as a byproduct under the influence of bulky phosphine ligand P(t-Bu)(3)center dot HBF4.
TETRAHEDRON LETTERS
(2021)
Article
Engineering, Environmental
Udayakumar Veerabagu, Zhaobin Chen, Jiao Xiang, Zihua Chen, Mingen Liu, Hong Xia, Fushen Lu
Summary: A novel Pd@carbon composite derived from cigarette butts was successfully prepared and exhibited improved dispersion and stability of Pd nanoparticles for the Suzuki-Miyaura cross-coupling reaction. The work not only addresses environmental concerns but also offers insights into the valorization of high-performance carbon nanomaterials at low cost and in large quantities.
JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING
(2021)
Article
Chemistry, Multidisciplinary
Yanir Kadosh, Yeshayahu Ben-Eliyahu, Yair Bochlin, Lior Ezuz, Yacov Iflah, Shuli Halevy, Sebastian Kozuch, Eli Korin, Armand Bettelheim
Summary: Oxidation of methane to useful oxygenates at a bilayer-coated electrode is achieved. The composition of the coating allows a cascade of oxygen transfer events, leading to the observation of formate and methanol at specific potential range.
CHEMICAL COMMUNICATIONS
(2022)
Editorial Material
Chemistry, Multidisciplinary
Renana Gershoni-Poranne, Ehud Keinan, Sebastian Kozuch
ISRAEL JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jan M. L. Martin
Summary: This article discusses the importance of electron correlation in chemistry, proposes a classification of correlation effects, and explores how DFT can shed light on wavefunction theory. Additionally, it introduces two types of honorary valence orbitals and the significance of atomization energies.
ISRAEL JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Nisha Mehta, Golokesh Santra, Jan M. L. Martin
Summary: The effect of F12 geminals on basis set convergence of harmonic frequencies calculated using B2GP-PLYP and revDSD-PBEP86-D4 double-hybrid density functionals was investigated. The cc-pVDZ-F12 basis set is close to the complete basis set (CBS) limit even with a two zeta step acceleration, indicating that the convergence problem is not as severe as that for energetics. Conventional orbital calculations with augmented triple zeta quality basis set are acceptably close to the CBS limit for harmonic frequencies.
CANADIAN JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Noy B. Nechmad, Keren Iudanov, Naziha Tarannam, Victoria Kobernik, Sebastian Kozuch, N. Gabriel Lemcoff
Summary: The ruthenium alkylidene-catalyzed ring-closing metathesis (RCM) of 5-membered rings is highly favored due to entropic and enthalpic contributions. However, the RCM of a hindered diene could only be achieved at high concentrations using a trifluoromethyl sulfur-chelated ruthenium benzylidene catalyst. The addition of ethyl acetate significantly enhanced the catalyst's activity.
Article
Chemistry, Multidisciplinary
Alex Blahman, Sebastian Kozuch
Summary: This article describes a previously unheard of type of coordinating bond, and computationally investigates one such case involving a borabenzene ligand and a bismuth pincer complex. The study suggests that inverse bonding-backbonding (IBBB) involving d orbitals in transition metals is impossible, but a pi charge transfer to a post-transition metal empty p orbital can achieve it.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zayed Alassad, Ashim Nandi, Sebastian Kozuch, Anat Milo
Summary: Secondary-sphere interactions have been used to control reactivity and selectivity in organometallic and enzymatic catalysis. This study investigates the mechanistic pathway promoted by secondary-sphere modification in organocatalysis using boronic acids as modifiers. The results indicate stable off-cycle catalyst aggregation and BA-base adducts, and a rate-limiting, water-assisted hydrogen atom transfer mechanism. The presence of secondary-sphere modifiers also leads to an uncommon Curtin-Hammett-controlled enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Itzhak Sedgi, Sebastian Kozuch
Summary: In this study, we computationally analyzed the structure, thermodynamics, and kinetics of substitutional nitrogen, boron, and oxygen in diamond at different scales, focusing on the possibility of heavy atom quantum tunnelling rearrangement between isomers. The results revealed intriguing behaviors such as thermally activated tunnelling of nitrogen, which depends on cage size, and quantum delocalization of boron. Moreover, we predicted that the thermodynamics and kinetics of rearrangement can be controlled through tunnelling by applying an external electric field, suggesting the potential use of these systems as atomic memory devices.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Irena Efremenko, Jan M. L. Martin
Summary: A detailed study of C-sp2-H activation in benzene and methyl acrylate by the RuClm(CO)(n) catalyst is presented using density functional theory (DFT) and coupled cluster methods. The results show that the coupled cluster calculations are quantitatively consistent with experiments. The Ru(II) and Ru(III) catalyst precursors transform into the same active form of the catalyst, explaining the experimental results. Oxidative addition is unfavorable, especially in the presence of CO.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Axel D. Becke, Golokesh Santra, Jan M. L. Martin
Summary: In two recent papers, we compared two Kohn-Sham density functionals based on physical modeling and theory with the best density-functional power-series fits in the literature. The best error statistics reported so far for a hybrid functional on the GMTKN55 chemical database were obtained. In this work, additional second-order perturbation-theory terms are considered, resulting in a 12-parameter double-hybrid density functional with the lowest GMTKN55 WTMAD2 error yet seen.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Nisha Mehta, Jan M. L. Martin
Summary: It is necessary to use additional tight (high-exponent) d functions in wave function ab initio and DFT calculations for second-row compounds, such as the cc-pV(n+d)Z and aug-cc-pV(n+d)Z basis sets, to achieve proper convergence. A similar phenomenon exists for the isovalent compounds of the heavy p-block, where tight f functions are needed to enhance the description of the low-lying 4f and 5f Rydberg orbitals.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Naziha Tarannam, Nebal Alassad, N. Gabriel Lemcoff, Sebastian Kozuch
Summary: A layered meta-benchmarking analysis was conducted to demonstrate a protocol for method selection and estimation of Gibbs energies of catalytically prominent reactions. The study focused on the active-latent equilibrium of two metathesis catalysts and utilized a computational benchmark for gas phase energies, followed by benchmarking enthalpy and Gibbs energy from experimental references. The results indicated the effectiveness of certain reference methods, the accuracy of specific functionals, and the importance of solvation models and entropy in the estimation of Gibbs energy.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Organic
Partha Jyoti Das, Ankana Roy, Ashim Nandi, Ishita Neogi, Yael Diskin-Posner, Vered Marks, Iddo Pinkas, Sara Amer, Sebastian Kozuch, Michael Firer, Michael Montag, Flavio Grynszpan
Summary: In this study, a series of thioxobimanes were synthesized and extensively characterized. The potential of these compounds as ligands for transition metals was demonstrated.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Rahul Shukla, Dongkun Yu, Tiancheng Mu, Sebastian Kozuch
Summary: Most studies on hole interactions (HIs) have focused on understanding the nature and characteristics of sigma and pi-holes. However, this perspective explores the origin and properties of lone-pair holes, which are present on an atom opposite to its lone-pair region. By examining various molecular systems, including X3N/PMIDLINE HORIZONTAL ELLIPSISF- (X = F/Cl/Br/I), F-Cl/Br/IMIDLINE HORIZONTAL ELLIPSISH3PMIDLINE HORIZONTAL ELLIPSISNCH, and H3B-NBr3, it is investigated to what extent these lp-holes participate in lp-hole interactions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Golokesh Santra, Emmanouil Semidalas, Nisha Mehta, Amir Karton, Jan M. L. Martin
Summary: The S66x8 noncovalent interactions benchmark has been re-evaluated using different methods and considering different basis sets and truncation error corrections. The study found that the LNO-CCSD(T) method performs well under very tight criteria, but struggles with complex counterpoise corrections. In contrast, the PNO-LCCSD(T) method performs best with counterpoise corrections.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
