Article
Chemistry, Multidisciplinary
Huaipu Yan, Qian Liao, Yuqing Chen, Gagik G. G. Gurzadyan, Binghui Lu, Chao Wu, Lei Shi
Summary: Co-porphines were discovered to be highly efficient MHAT catalysts for chemoselective allene functionalization under photoirradiation with a loading of only 0.01 mol %. The combination of photo Co-MHAT and Ti catalysis enabled successful carbonyl allylation, providing expedient access to beta-functionalized homoallylic alcohols in over 100 examples with exceptional regio- and diastereoselectivity. Mechanism studies supported the key role of selectively transferring hydrogen atoms from cobalt hydride to allenes and generating allyl radicals in the catalytic cycle.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Chenguang Yu, Peng Ji, Yueteng Zhang, Xiang Meng, Wei Wang
Summary: This method utilizes a cascade cocatalysis strategy to achieve the easy construction of chiral gamma, gamma-disubstituted butenolides, showing good generality and effectiveness.
Article
Chemistry, Multidisciplinary
Akira Saito, Shinya Adachi, Naoya Kumagai, Masakatsu Shibasaki
Summary: The strategic use of a sterically demanding Ni-II pincer carbene complex has enabled high enantioselectivity in the direct catalytic asymmetric addition of acetonitrile to aldehydes, resulting in highly enantioenriched beta-hydroxynitriles. This highly atom-economical process offers a promising pathway for utilizing inexpensive acetonitrile as a C2 building block in practical synthetic toolbox for asymmetric catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Raul Porcar, Eduardo Garcia-Verdugo, Belen Altava, Maria Isabel Burguete, Santiago V. Luis
Summary: Chiral imidazolium l-prolinate salts have been studied as green and efficient chiral organocatalysts for direct asymmetric aldol reactions at room temperature. The presence of chirality in both the imidazolium cation and prolinate anion plays a significant role in transferring chirality from the organocatalyst to the aldol product. By selecting proper structural elements in the cation and anion, excellent activities, selectivities, and enantioselectivities can be achieved.
Review
Chemistry, Multidisciplinary
Yuji Nakano, Jeremy T. Maddigan-Wyatt, David W. Lupton
Summary: Conjugate acceptors are commonly used electrophilic functional groups in organic synthesis. Our research focuses on their ability to undergo polarity inversion through the conjugate addition of Lewis base catalysts. We have achieved cycloisomerizations and annulation reactions using simple conjugate acceptors and those embedded within more complicated substrates. However, significant challenges remain to be addressed before a universal approach to polarity inversion of all conjugate acceptors can be achieved.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Stuart C. D. Kennington, Saul F. Teloxa, Miguel Mellado-Hidalgo, Oriol Galeote, Sabrina Puddu, Marina Bellido, Pedro Romea, Felix Urpi, Gabriel Aullon, Merce Font-Bardia
Summary: A direct and asymmetric aldol reaction of N-acyl thiazinanethiones with aromatic aldehydes catalyzed by chiral nickel(II) complexes was reported. The reaction gives high yields of O-TIPS-protected anti-aldol adducts with remarkable stereocontrol and atom economy. The removal of the achiral scaffold provides enantiomerically pure intermediates with synthetic interest for producing anti-alpha-amino-beta-hydroxy and alpha,beta-dihydroxy carboxylic derivatives, with theoretical calculations explaining the observed high stereocontrol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Tasneem Elkoush, Natasha D. Reich, Michael G. Campbell
Summary: In the past two decades, there has been a significant increase in the number of synthetically useful transformations catalyzed by silver, with dinuclear silver species commonly emerging as a key feature in these reactions. Understanding the role of dinuclear silver complexes in homogeneous catalysis can aid in the development of improved design principles for silver catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Shinya Adachi, Akira Saito, Masakatsu Shibasaki
Summary: This study reports a method for direct catalytic asymmetric reactions of alkylnitriles and imines. By adding specific catalysts and additives, high yields, high anti/syn diastereoselectivities, and high enantiomeric ratios can be achieved.
Article
Chemistry, Organic
Ninghui Zhang, Chunli Zhang, Xiaoping Hu, Xin Xie, Yuanhong Liu
Summary: An efficient nickel-catalyzed addition of benzyl nitriles to terminal vinyl ketones via C(sp(3))-H functionalization has been developed, providing a novel protocol for the synthesis of α-functionalized benzyl nitriles with structural diversity under mild reaction conditions without the use of a strong base. This work might be potentially useful towards the development of an enantioselective variant using chiral nitrogen ligands.
Article
Chemistry, Organic
Shuma Sasaki, Jun Kikuchi, Shingo Ito, Naohiko Yoshikai
Summary: In this study, a method for preparing stereodefined enolates by leveraging the stereoselective oxyfunctionalization of unactivated alkynes and their reaction with aldehydes to form γ,δ-unsaturated β-diketones was described.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Minghui Zhu, Peixin Wang, Qinglong Zhang, Wenjun Tang, Weiwei Zi
Summary: The aldol reaction is an important and versatile transformation in organic synthesis, but achieving stereoselectivity for the formation of diastereomeric products is challenging. In this study, a new catalytic system was developed to overcome the selectivity limitations of the reaction. Computational studies provided insights into the reaction mechanism and stereochemistry of the catalytic system.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Daniel Timelthaler, Christoph Topf
Summary: This study presents a simple method for the transfer hydrogenation of aromatic aldehydes in i-PrOH using the cost-effective and easy-to-handle [Cr(CO)(6)] as a catalyst. The reactions can be carried out in normal atmosphere without the need for special equipment, and various functional groups are tolerated. Furthermore, the addition of TMAO can further promote the catalytic transformations. This method is also suitable for processing thermo-labile substrates.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Organic
Emanuele Pinosa, Andrea Gualandi, Andrea Fermi, Paola Ceroni, Pier Giorgio Cozzi, Francesco Calogero
Summary: A dual photoredox- and titanocene-catalyzed methodology for the regioselective access to alpha-vinyl-beta-hydroxy esters towards aldehyde allylation with 4-bromobut-2-enoate is reported. The protocol ensures a better regioselectivity and avoids the use of specific metal reagents.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Wei-Dong Lu, Yu Zheng, Zhi-Peng Zhang, Hong-Bin Chen, Kai Chen, Hao-Yue Xiang, Hua Yang
Summary: In this study, a visible-light-induced palladium-catalyzed desaturation/sulfonation cascade is reported, providing a concise method for the synthesis of highly valuable 4-sulfonyltetrahydropyridine scaffolds from inexpensive and readily available piperidine derivatives with sodium sulfinates. The success of this transformation relies on the well-designed sequence of palladium-mediated 1,5-hydrogen atom transfer/β-hydride elimination/allylic sulfonation process, highlighting the potential of orchestrating synthetic events through rational utilization of varied catalytic modes.
Article
Chemistry, Multidisciplinary
Yuqing Chen, Huaipu Yan, Qian Liao, Dandan Zhang, Shuangjie Lin, Erjun Hao, Rukhsana Murtaza, Chenchen Li, Chao Wu, Chunying Duan, Lei Shi
Summary: In this study, we present a metal-free radical cross-coupling strategy for the synthesis of homoallyl amines. This method involves the reaction between an alpha-amino alkyl radical and a transient allylic radical to obtain homoallyl amines from readily available materials. The method exhibits excellent regioselectivity and broad functional group compatibility.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
