Article
Chemistry, Organic
Ksenia S. Stankevich, Matthew J. Cook
Summary: The Hosomi-Sakurai reaction is a crucial transformation for the creation of complex carbon-cyclic systems. These methods are capable of generating significant stereochemical complexity in a single step and have been extensively used in the total synthesis of carbon-rich natural products. This review focuses on the application of this approach in carbocyclization reactions, where the formed C-C bond is incorporated into an all-carbon cyclic system, with particular emphasis on stereochemical selectivity.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Organic
Airat M. Gimazetdinov, Mansur S. Miftakhov
Summary: A new intramolecular variant of the Hosomi-Sakurai reaction was reported, which involves the generation of methoxy methylene carbocation from enol ether and its subsequent attack on the allylsilane moiety. The aldehydes formed from the reaction undergo Hosomi-Sakurai cyclization, leading to epimeric alcohols of norbornene structure. The starting enol ether can undergo protodesilylation and hydrolysis selectively by treatment with TBAF, while giving a mixture of epimeric products of different topologies by treatment with BF3•Et2O.
TETRAHEDRON LETTERS
(2023)
Article
Biochemistry & Molecular Biology
Zubao Gan, Deyun Cui, Hongyun Zhang, Ying Feng, Liying Huang, Yingying Gui, Lu Gao, Zhenlei Song
Summary: The Hosomi-Sakurai allylation of allylsilanes with beta,gamma-unsaturated alpha-ketoesters has been successfully catalyzed by (Ph3C)[BPh((F))(4)] to afford gamma,gamma-disubstituted alpha-ketoesters in high yields and excellent chemoselectivity. Preliminary mechanistic studies indicate that the trityl cation is the major contributor to the catalysis, with the silyl cation playing a minor role.
Review
Chemistry, Applied
Dean D. Roberts, Mark G. McLaughlin
Summary: Organosilicon reagents are highly versatile and important, and the beta-Silicon effect allows them to undergo a variety of transformations. This review discusses the application of the beta-Silicon effect in various organic transformations, and provides examples in methodology development and natural product synthesis.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Felix Schaefers, Subhabrata Dutta, Roman Kleinmans, Christian Mueck-Lichtenfeld, Frank Glorius
Summary: A general strategy is reported in this paper to access a variety of valuable homoallylic alcohols with opposite chemo- and diastereoselectivity by switching to photocatalytic activation in combination with a closed transition state.
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
Dong-Xing Zhu, Jian-Guo Liu, Ming-Hua Xu
Summary: A one-pot reaction has been developed for the stereodivergent synthesis of diverse 2,3-disubstituted dihydrobenzofurans under mild conditions with high yields and stereoselectivity. By appropriate permutations of two chiral catalysts, a wide range of chiral products can be accessed, demonstrating the ability of two chiral catalysts to independently control two contiguous stereogenic centers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Bo-Bo Gou, Yue Tang, Yan-Hong Lin, Le Yu, Qing-Song Jian, Huai-Ri Sun, Jie Chen, Ling Zhou
Summary: A new type of chiral all-carbon tetrasubstituted VQMs was successfully prepared via nucleophilic addition of 2-alkynylnaphthols to o-quinone methides or imines, catalyzed by chiral phosphoric acids. The method showed high efficiency and excellent diastereoselectivities and enantioselectivities, leading to the synthesis of naphthyl-2H-chromenes with axially and centrally chiral elements and axially chiral quinone-naphthols. The obtained axially chiral naphthols could further be converted into valuable phosphine ligands and other functional molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Si-Qing Wang, Zong-Ci Liu, Wen-Jun Yue, Liang Yin
Summary: This study reveals a vinylogous aldol-type reaction for the synthesis of chiral gamma-hydroxyl-alpha,beta-unsaturated azaarenes with high selectivity and yields. The use of different ligands can control the formation of the carbon-carbon double bond in the products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Paul Zebrowski, Uwe Monkowius, Mario Waser
Summary: We report a two-step approach for the enantioselective synthesis of novel chiral δ-lactams. The protocol involves an asymmetric α-allylation of activated aryl esters followed by an acid-mediated lactam formation. The method provides highly enantioselective and reasonably high-yielding products, which can be further utilized via transformations of the exocyclic double bond.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Dian-Feng Chen, Liu-Zhu Gong
Summary: This article introduces the fundamental attributes of asymmetric organo/transition-metal combined catalysis (AOMC), explains how organocatalysts and transition-metal complexes collaborate, and discusses future opportunities in this field.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Qingqing Luo, Zhou Tian, Jie Tang, Jie Wang, Yin Tian, Cheng Peng, Gu Zhan, Bo Han
Summary: The study focuses on the design of bifunctional 4-pyrrolidinopyridines as Lewis base catalysts, which exhibited excellent efficiency and stereoselectivity in asymmetric cycloaddition reactions. The research provides strong support for the construction of chiral spiropyrazolone derivatives.
Article
Chemistry, Physical
Pierpaolo Morgante, Coty Deluca, Tegla E. Jones, Gregory J. Aldrich, Norito Takenaka, Roberto Peverati
Summary: This study investigates the mechanism of allylation reactions of aldehydes under catalytic conditions, and evaluates the applicability of 34 different density functional methods. The results show that only functional methods accounting for dispersion interactions correctly can provide consistent outcomes.
Article
Chemistry, Organic
Lukas Schober, Fabio Tonin, Ulf Hanefeld, Harald Groeger
Summary: A sequential-type and tandem-type chemoenzymatic flow cascade has been developed to selectively form a 1,3-diol with two stereogenic centers. Both sequential and tandem flow approaches have demonstrated high conversion rates and enantiomeric excess.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Fen Tan, Xiao-Yu He, Qing-Qing Yang, You-Quan Zou
Summary: This short review covers the recent synthetic aspects of 3-isothiocyanato oxindoles participated cascade cyclizations, with a focus on formal [3+2] cycloaddition reactions.
Article
Chemistry, Physical
Hao Chen, Arup Mondal, Philipp Wedi, Manuel van Gemmeren
Article
Chemistry, Organic
Kiron K. Ghosh, Alexander Uttry, Aylin Koldemir, Mike Ong, Manuel van Gemmeren
Review
Chemistry, Organic
Alexander Uttry, Manuel van Gemmeren
SYNTHESIS-STUTTGART
(2020)
Article
Chemistry, Multidisciplinary
Hao Chen, Mirxan Farizyan, Francesca Ghiringhelli, Manuel van Gemmeren
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Kiron Kumar Ghosh, Alexander Uttry, Arup Mondal, Francesca Ghiringhelli, Philipp Wedi, Manuel van Gemmeren
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Review
Chemistry, Organic
Hao Chen, Mirxan Farizyan, Manuel van Gemmeren
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Review
Chemistry, Organic
Johannes E. Erchinger, Manuel van Gemmeren
Summary: This article discusses the combination of electrochemistry and Pd-catalyzed C-H activation/functionalization to achieve C-C, C-X, C-O, and C-P bond formation.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Arup Mondal, Manuel van Gemmeren
Summary: Alkynes are important motifs in organic synthesis due to their presence in natural products and bioactive molecules. The method of inserting alkynes into (hetero)arenes relies heavily on the regioselectivity of the halogenation step, and can achieve selective alkynylation of thiophenes. The developed palladium-catalyzed C-H activation/alkynylation of thiophenes allows for regiodivergent reactions and late-stage modifications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Francesca Ghiringhelli, Alexander Uttry, Kiron Kumar Ghosh, Manuel Van Gemmeren
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Editorial Material
Chemistry, Multidisciplinary
Sabine Bognar, Manuel van Gemmeren
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Sabine Bognar, Manuel van Gemmeren
Summary: A synthetically simple general one-step protocol was developed for the selective synthesis of a broad range of unsymmetrical dithioacetals consisting of one aromatic and one aliphatic thiol moiety. The mixed S,S-acetals were obtained in high yields, demonstrating excellent selectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Philipp Wedi, Mirxan Farizyan, Klaus Bergander, Christian Mueck-Lichtenfeld, Manuel van Gemmeren
Summary: Recent discovery of palladium catalysts has enabled direct-group-free C-H activation of arenes without excess substrate, allowing for late-stage modification of complex organic molecules. The success lies in the use of two complementary ligands, N-acyl amino acid and N-heterocycle. Mechanistic studies have identified catalytically active species and a transition state model that explains the exceptional activity and selectivity of these catalysts, with potential for further method development.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Alexander Uttry, Sourjya Mal, Manuel van Gemmeren
Summary: The study describes the late-stage deuteration of free carboxylic acids and enables the functionalization of non-activated methylene beta-C(sp(3))-H bonds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Carlos Santiago, Hao Chen, Arup Mondal, Manuel van Gemmeren
Summary: In this study, dual ligand-based palladium catalysts were used for late-stage olefination of arenes, successfully functionalizing complex arene substrates. The method utilizes the arene as a limiting reactant and controls the regioselectivity of the transformation by the steric and electronic properties of the substrate, providing a new pathway for preparing regioisomers.
Article
Chemistry, Organic
Manuel van Gemmeren, Benjamin List
Summary: This article details the development of Select Crowd Reviewing from the initial idea through a pilot phase to its current status as the default method for evaluating manuscripts at Synlett and SynOpen. The workflow for manuscript evaluation using Select Crowd Reviewing is described, along with a discussion of the advantages it offers compared to traditional peer review.
