Article
Chemistry, Multidisciplinary
Francis Bru, Mathieu Lesieur, Albert Poater, Alexandra M. Z. Slawin, Luigi Cavallo, Catherine S. J. Cazin
Summary: The synthesis and isolation of [Pd(NHC)(PhC equivalent to CPh)] complexes were reported, which are new 14-electron Pd(0)-complexes that serve as key synthons for known palladium(0) and palladium(II) species and allow access to unprecedented mixed NHC-phosphite palladium(0) complexes. These complexes are also capable of catalyzing the facile hydrosilylation of allenes. DFT calculations provided insights into the relatively weak interaction between the metal and the diphenylacetylene ligand, comparing it with other ligands with varying coordinating power, structure, and electronic properties.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Tobias Wagener, Lukas Lueckemeier, Constantin G. Daniliuc, Frank Glorius
Summary: This study successfully demonstrates the synthesis of sought-after, enantioenriched delta-lactams through an interrupted hydrogenation mechanism using oxazolidinone-substituted pyridines and water.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Yasuaki Fukazawa, Vladimir Yu. Vaganov, Julia V. Burykina, Artem N. Fakhrutdinov, Ruslan I. Safiullin, Felix Plasser, Aleksandr E. Rubtsov, Valentine P. Ananikov, Andrei V. Malkov
Summary: The mechanism of metal-catalyzed asymmetric alkylation of indoles remains uncertain. In this study, the authors investigate the mechanism from both molecular and nano-level perspectives, revealing the role of water and catalyst precursor on reaction selectivity and performance.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
David P. Tilly, William Cullen, Heng Zhong, Romain Jamagne, Inigo Vitorica-Yrezabal, Simon J. Webb
Summary: By investigating the effect of remotely induced changes in ligand folding, a potential pathway towards remote conformational control of organometallic catalysts has been discovered. The study on dynamic folding of Aib peptides revealed that the chiral conformational preference of N-terminal residues can be relayed to the axially chiral Rh(NHC) complex in the helical body.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Akin Mumcu, Mert Olgun Karatas, Namik Ozdemir, Ali Erdogan, Hasan Kucukbay
Summary: In this study, complexes [Ru(NHC)(p-cymene)Cl-2], [MCl(NHC)(cod)] (M=Rh or Ir), and [RhCl(NHC)(CO)(2)] have been synthesized and characterized. The catalytic activity of these complexes in hydrosilylation of terminal alkynes has been investigated. Among them, Ir-NHC exhibited high conversion rate and β-(Z) selectivity, while Rh-NHC showed β-(Z) selectivity initially but isomerized to β-(E) isomer after 24 hours. The results indicate the potential application of these complexes in catalytic reactions.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Tobias Wagener, Marco Pierau, Arne Heusler, Frank Glorius
Summary: In this study, a one-pot protocol for the synthesis of octahydroindoles, decahydroquinolines, and octahydroindolizines through a cascade reaction is presented.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Yu-Hao Huang, Yichen Wu, Zile Zhu, Sujuan Zheng, Zihang Ye, Qian Peng, Peng Wang
Summary: This study demonstrated an asymmetric synthesis method for monohydrosilanes via intramolecular hydrosilylation strategy, with high diastereo-, regio-, and enantioselectivities, including chiral oxasilacycles. The catalyst loading could be reduced to 0.1 mol %, making it one of the most efficient methods for accessing chiral monohydrosilanes. Mechanistic studies suggest a Chalk-Harrod mechanism for the Rh-catalyzed intramolecular asymmetric hydrosilylation reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Ying Wang, Zi-Lu Wang, Wei-Wei Ma, Yun-He Xu
Summary: A copper-catalyzed regioselective Markovnikov 3,4-hydrosilylation of 2-substituted 1,3-dienes has been successfully achieved. A wide range of 2-substituted 1,3-dienes and trihydrosilanes are compatible under the optimal conditions. The use of a bisphosphine ligand with a rigid backbone provides the Markovnikov 3,4-hydrosilylation product with better yield and selectivity. Additionally, the synthetic utilities of the allylsilanes were demonstrated through their flexible derivatizations.
Article
Chemistry, Multidisciplinary
Ella J. Watkins-Dulaney, Noah P. Dunham, Sabine Straathof, Soma Turi, Frances H. Arnold, Andrew R. Buller
Summary: The engineered TrpB enzyme can catalyze the asymmetric alkylation of ketones, addressing a significant challenge in synthetic chemistry. Through directed evolution, high selectivity is achieved in the alkylation of propiophenone and 2-fluoroacetophenone. Control over stereochemistry at the new chiral center is demonstrated, showing potential for efficient synthesis of non-canonical prolines and other chirally dense nitrogen heterocycles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Cai Zhang
Summary: This review comprehensively summarizes the application of bisphospholane Josiphos-type ligands in rhodium asymmetric catalysis, including asymmetric addition, asymmetric hydrogenation, and asymmetric silanization reactions.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Florian Lind, Armido Studer
Summary: Acylsilanes, a class of organosilicon compounds, have been gaining increased attention due to their ability to generate carbenes and their usefulness as reagents in organic synthesis. In this study, a novel and efficient route for the synthesis of acylsilanes was reported through alkene hydrosilylation. By using acylhydrosilanes as silylation reagents in rhodium catalyzed alkene hydrosilylations, a wide range of acylsilanes can be accessed in good to excellent yields under mild conditions with high functional group tolerance and atom economy.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Bincy Chindan, Anagha Syam, Hariharan Mahendran, Ramesh Rasappan
Summary: In this study, a method for synthesizing α-vinyltrialkoxysilanes via cross-electrophile C(sp(2))-C(sp(2)) coupling was reported. The method demonstrates high compatibility with functional groups under milder reaction conditions.
Article
Chemistry, Inorganic & Nuclear
Javier Ruiz, Maria A. Mateo
Summary: An isocyanide-functionalized imidazole was synthesized from 4-(1H-imidazol-1-yl)aniline using the Ugi method, and subsequently converted into the corresponding imidazolium salt. Coordination of the isocyanide residue allowed the synthesis of several transition metal complexes containing a peripheral imidazolium cation, which serve as suitable starting materials for the formation of mixed ligand isocyanide-NHC heterometallic complexes.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Physical
Vidmantas Bieliunas, Sigitas Stoncius
Summary: The design and synthesis of second generation C-2-symmetric ligands with additional substituents was reported. These substituents provide a further element for fine-tuning the ligand structure by enforcing conformational rigidity. The tetrasubstituted bicyclo[3.3.1]nona-2,6-dienes were successfully employed in the rhodium-catalyzed arylation reaction with good to excellent yields and enantioselectivities up to 99% ee.
Article
Chemistry, Multidisciplinary
Xin Liu, Li-Gao Liu, Can-Ming Chen, Xiao Li, Zhou Xu, Xin Lu, Bo Zhou, Long-Wu Ye
Summary: [2,3]-Sigmatropic rearrangement reaction involving sulfonium ylide (Doyle-Kirmse reaction) generated from metal carbenes is a powerful method for the construction of C(sp(3))-S and C-C bonds. However, asymmetric versions using sulfonium ylides from metal carbenes as precursors have been rarely reported, and limited to diazo compounds. Here, we present a copper-catalyzed enantioselective Doyle-Kirmse reaction via azide-ynamide cyclization, providing chiral [1,4]thiazino[3,2-b]indoles with a quaternary carbon stereocenter in moderate to excellent yields and excellent enantioselectivities. Importantly, this protocol represents a unique catalytic asymmetric Doyle-Kirmse reaction through a non-diazo approach and an unprecedented asymmetric [2,3]-sigmatropic rearrangement via alpha-imino metal carbenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)