Article
Chemistry, Physical
Jian-Hua Liu, Qing Zhou, Yao Lin, Zhu-Lian Wu, Tian Cai, Wei Wen, Yan-Min Huang, Qi-Xiang Guo
Summary: In this study, a highly efficient atom-economic asymmetric alpha-allylation method using chiral-aldehyde/palladium catalyst was reported. This method enables the asymmetric alpha-allylation of different 1,3-dienes and allenes with N-unprotected amino acid esters, leading to the synthesis of alpha,alpha-disubstituted chiral alpha-amino acid esters with high efficiency, good yields, and stereoselectivities. No N-allylation byproducts were observed in these reactions. Two reaction models were proposed based on mechanistic control experiments. Overall, this work demonstrates a new approach for preparing structurally diverse chiral amino acids and provides insights for developing chiral-aldehyde catalytic systems.
Article
Chemistry, Multidisciplinary
Jun-Jie Tian, Rui-Rui Li, Gui-Xiu Tian, Xiao-Chen Wang
Summary: Here, we describe a new method for enantioselective C-H allylation of pyridines at C3 using a tandem borane and palladium catalysis. This method involves borane-catalyzed pyridine hydroboration, palladium-catalyzed enantioselective allylation of the resulting dihydropyridines with allylic esters, and air oxidation to afford the products. This method allows for the introduction of an allylic group at C3 with excellent regio- and enantioselectivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xian-Xiao Chen, Hao Luo, Ye-Wei Chen, Yang Liu, Zhi-Tao He
Summary: Chain walking has been an efficient method for the functionalization of inert C(sp(3))-H bonds, but it has limitations on mono-olefin migration and functionalization. In this study, we demonstrate the feasibility of tandem directed simultaneous migrations of remote olefins and stereoselective allylation. The use of palladium hydride catalysis and secondary amine morpholine as a solvent is crucial for achieving high substrate compatibility and stereochemical control.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Pu-Sheng Wang, Liu-Zhu Gong
Summary: Pd-catalyzed asymmetric allylic C-H functionalization is a powerful tool to access chiral and densely functionalized molecules from easily accessible alkenes, resulting in increased step- or atom-economy by minimizing functional group manipulations. However, due to inadequate stereoselection strategies, this field is still in its early stage. This essay describes the journey to identify asymmetric catalytic systems, the mechanism of allylic C-H activation, control of stereo- and regioselectivity, and applications in asymmetric synthesis.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Jun Zheng, Christoph Nopper, Rifhat Bibi, Ali Nikbakht, Felix Bauer, Bernhard Breit
Summary: A dual photoredox/nickel catalyzed method for the regio- and diastereoselective allylation of N-aryl alpha-amino acids is presented. The reaction provides branched homoallylic amines in high yields and high syn-diastereoselectivity under mild and redox-neutral conditions. The broad substrate scope and high functional group tolerance demonstrate the synthetic flexibility of this reaction.
Article
Chemistry, Applied
Yoshikazu Horino, Mayo Ishibashi, Juri Sakamoto, Miki Murakami, Toshinobu Korenaga
Summary: The diastereoselective synthesis of anti-homoallylic alcohols bearing conjugated (Z)-enynes through a palladium-catalyzed three-component reaction is described, featuring a broad substrate scope, good functional group compatibility, and high levels of (Z)-alkene stereocontrol. The reaction involves Pd(0) functioning as a catalyst in two fundamental steps: the generation of a borylated pi-allylpalladium species inducing umpolung allylation of aldehydes, and C(sp(2))-C(sp) cross-coupling. Further transformations of the obtained products highlight their synthetic utility.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Simon Sieger, Ilja Lubins, Bernhard Breit
Summary: A highly versatile palladium-catalyzed allylation reaction has been reported, providing a waste-free access to allylated nucleophiles with unlimited possibilities for further functionalization. The reaction can be conducted using propadiene in toluene, and the mechanism is supported by deuterium labeling experiments.
Article
Chemistry, Physical
Simon V. Sieger, Ilja Lubins, Bernhard Breit
Summary: A highly versatile palladium-catalyzed allylation reaction using various pronucleophiles has been reported. Through the use of propadiene in toluene, this reaction provides an efficient and waste-free method to obtain allylated nucleophiles with unlimited potential for further functionalization. The Pd/BINAP system is not only capable of adding N-, O-, and S-pronucleophiles, but also C-pronucleophiles to allene. The plausible mechanism is supported by deuterium labeling experiments.
Article
Multidisciplinary Sciences
Guogang Deng, Shengzu Duan, Jing Wang, Zhuo Chen, Tongqi Liu, Wen Chen, Hongbin Zhang, Xiaodong Yang, Patrick J. Walsh
Summary: In this study, a transition-metal-free allylation strategy with allyl ether electrophiles is demonstrated to form homoallylic amine derivatives in up to 92% yield, providing valuable insights into C(sp(3))-C(sp(3)) bond-forming reactions.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Zhi-Zhou Pan, Jia-Heng Li, Hu Tian, Liang Yin
Summary: A copper(I)-catalyzed asymmetric allylation of ketones with 2-aza-1,4-dienes has been demonstrated, providing a series of functionalized homoallyl tertiary alcohols with high to excellent enantioselectivity. The deprotonation of N-allyl-1,1-diphenylmethanimines is the rate-determining step in the reaction, generating nucleophilic allyl copper(I) species. The utility of this method has been demonstrated by the asymmetric synthesis of (R)-boivinianin A and (R)-gossonorol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jose A. Carmona, Patricia Rodriguez-Salamanca, Rosario Fernandez, Jose M. Lassaletta, Valentin Hornillos
Summary: An atroposelective Ir-catalyzed dynamic kinetic resolution (DKR) of 2-(quinolin-8-yl)benzaldehydes/1-naphthaldehydes is achieved by transfer hydrogenative coupling of allyl acetate. The reaction leads to the installation of central and axial chirality, with high diastereoselectivities and excellent enantioselectivities when ortho-cyclometalated iridium-DM-BINAP is used as the catalyst. The racemization of the substrates is facilitated through a designed transient Lewis acid-base interaction between the quinoline nitrogen atom and the aldehyde carbonyl group.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Ting Yu, Zhong-Qiu Li, Jing Li, Sidi Cheng, Jiali Xu, Jun Huang, Yu-Wu Zhong, Shuang Luo, Qiang Zhu
Summary: Enantioenriched pyrido[6]helicenes and furan-containing pyrido[7]helicenes have been synthesized through a palladium-catalyzed double imidoylative cyclization. This method allows for the construction of two pyridyl rings in one pot, leading to structurally diverse optically pure pyridohelicenes. This research provides potential for optical studies and applications of this important class of azahelicenes.
Article
Chemistry, Organic
Zheye Zhang, Jiaining Liu, Shang Gao, Bo Su, Ming Chen
Summary: We describe the stereoselective syntheses of (E)- and (Z)-crotylboronates with alpha,alpha-disubstitution. The alkylation reaction exclusively occurs at the alpha position to the boryl groups in the starting crotylboronates, resulting in the desired boronates while maintaining the original alkene geometries. The resulting alpha,alpha-disubstituted crotylboronates can undergo aldehyde addition to afford allylated products with high stereoselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Kristina Plevova, Peter Kisszekelyi, Denisa Vargova, Samuel Andrejcak, Viktor Toth, LukaS Fertal, Erik Rakovsky, Juraj Filo, Radovan Sebesta
Summary: This study demonstrates the diastereoselective double C-H heteroarylation of chiral ferrocenes using Pd-complexes with chiral mono-protected amino acids, resulting in a variety of functionalized compounds. The absolute configurations of CH-activation products were confirmed using X-ray crystallographic analysis and CD spectroscopy, while insights into the reaction mechanism and stereoinduction were provided by F-19 NMR kinetic study and DFT calculations.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Sijing Xue, Alexander Lucht, Jordi Benet-Buchholz, Arjan W. Kleij
Summary: The challenging metal-catalyzed asymmetric synthesis of highly functional quaternary carbon centers using decarboxylative C(sp(3))-C(sp(3)) bond formation reactions has been successfully reported in this study. By activating a key substrate, a vinyl cyclic carbonate, both the requisite nucleophile and electrophile reaction partner were provided for the asymmetric cross-coupling process. Through extensive screening of reaction conditions, additives and catalyst precursors, a protocol was developed that allowed access to a series of compounds featuring densely functionalized, elusive quaternary carbon stereocenters in appreciable yield and with enantiomeric ratios (er's) of up to 90 : 10.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Tomoya Miura, Junki Nakahashi, Takanori Sasatsu, Masahiro Murakami
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Chemistry, Organic
Tomoya Miura, Daisuke Moriyama, Yuuta Funakoshi, Masahiro Murakami
Article
Chemistry, Multidisciplinary
Tomoya Miura, Takayuki Nakamuro, Yuuya Nagata, Daisuke Moriyama, Scott G. Stewart, Masahiro Murakami
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Organic
Kieran D. Jones, Michael J. Nutt, Elena Comninos, Alexandre N. Sobolev, Stephen A. Moggach, Tomoya Miura, Masahiro Murakami, Scott G. Stewart
Article
Chemistry, Multidisciplinary
Tomoya Miura, Takayuki Nakamuro, Yumi Ishihara, Yuuya Nagata, Masahiro Murakami
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Tomoya Miura, Daisuke Moriyama, Sho Miyakawa, Masahiro Murakami
Article
Chemistry, Multidisciplinary
Tomoya Miura, Kohei Hagiwara, Takayuki Nakamuro, Yuuya Nagata, Naoki Oku, Masahiro Murakami
Summary: A method for the synthesis of 3,5-disubstituted-1,2,4-triazoles from nitriles and 5-aryltetrazoles is described. The reaction involves ring-chain tautomerization, denitrogenation, and 1,3-dipolar cycloaddition to achieve regioselective formation of the desired triazoles.
Article
Chemistry, Multidisciplinary
Tomoya Miura, Naoki Oku, Yota Shiratori, Yuuya Nagata, Masahiro Murakami
Summary: A new method for constructing propionate-derived trisubstituted alkene motifs with stereoselectivity has been reported. The method involves the ruthenium(II)-catalyzed double-bond transposition of 1-substituted 1,1-di(pinacolatoboryl)-alk-3-enes to generate E isomers of anti-homoallylic alcohols, while using a dimeric palladium(I) complex leads to the formation of Z isomers. The motifs can be successfully applied to the syntheses of specific compounds.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Tomoya Miura, Shunsuke Moritani, Yota Shiratori, Masahiro Murakami
Summary: A unique method for the synthesis of substituted 1-naphthols through rhodium(ii)-catalysed ring-expansion reaction of 2-triazolyl-1-indanone derivatives is reported. The 1,2-acyl migration occurs with an intermediate alpha-imino rhodium carbenoid generated from the triazolyl moiety.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Tomoya Miura, Yumi Ishihara, Takayuki Nakamuro, Shunsuke Moritani, Yuuya Nagata, Masahiro Murakami
Summary: This study investigates the asymmetric cyclooligomerization of bifunctional monomers catalyzed by rhodium(II). The major products obtained are cyclic dimers with unique structures, and it is observed that these structures can undergo ring-flipping.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Naoki Oku, Masahiro Murakami, Tomoya Miura
Summary: This article introduces a Suzuki-Miyaura cross-coupling reaction of alpha-chloroacetates or alpha-chloroacetamides with arylboronic acids under visible-light irradiation, providing a mild method for the synthesis of alpha-arylacetates and alpha-arylacetamides. Additionally, the authors successfully synthesized a key intermediate of the plant hormone auxin, indole-3-acetic acid derivative, from 1-Boc-indole in two steps by combining an iridium-catalyzed C-H borylation and a palladium-catalyzed cross-coupling reaction.
Article
Chemistry, Multidisciplinary
Keiichi Irifune, Ken Yamazaki, Takayuki Nakamuro, Masahiro Murakami, Tomoya Miura
Summary: A ligand-controlled regiodivergence in Ni-catalyzed rearrangement of vinylcyclopropanes to 1,4- or 1,5-disubstituted cyclopentenes is reported. The 1,4- or 1,5-disubstituted cyclopentene is selectively obtained depending on the choice of ligands. Detailed kinetic studies and density functional theory calculations on the catalytic cycle revealed that the product selectivity is determined at the reductive elimination step from the six-membered η(1)-allyl intermediate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Naoki Oku, Tomoya Miura
Summary: A double C(sp3)-H functionalization of ethylarenes with alcohols and N- fluorobenzenesulfonimide is demonstrated. The reaction proceeds in three stages: (1) Cu-catalyzed benzylic alkoxylation of ethylarenes to give 1-(1-alkoxyethyl)benzenes; (2) The resulting 1-(1-alkoxyethyl)benzenes gradually convert into vinylarenes; (3) Cu-catalyzed amino-alkoxylation of the intermediary vinylarenes to yield arylethanolamines. This method introduces C-N and C-O bonds regioselectively at the homobenzylic and benzylic positions of ethylarenes.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Keito Fuke, Tomoya Miura
Summary: This study reports a regioselective approach for the 1,2-hydro(cyanomethylation) of unactivated aliphatic alkenes. A cyanomethyl radical is added onto alkenes to form alkyl radicals, which then undergo further reactions to produce one-carbon-extended nitriles.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
