Article
Chemistry, Multidisciplinary
Minami Odagi, Taisei Matoba, Keisuke Hosoya, Kazuo Nagasawa
Summary: The first enantioselective total syntheses of hasubanan alkaloid (-)-metaphanine and norhasubanan alkaloid (+)-stephadiamine have been reported. These syntheses involve diastereoselective oxidative phenolic coupling reaction and subsequent regioselective intramolecular aza-Michael reaction to efficiently construct the hasubanan skeleton with a quaternary stereogenic center at C13. Furthermore, based on a hypothesis regarding the biosynthetic pathway of (+)-stephadiamine, it was found that (-)-metaphanine can easily be converted to (+)-stephadiamine via an aza-benzilic acid type rearrangement reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Cheng Bi, Yu Wang, Chi He, Phil S. Baran
Summary: This paper reports a concise total synthesis of the complex guanidinium toxin KB343, achieved through a series of unusual chemoselective transformations and strategic skeletal reorganization. The absolute configuration is confirmed through an enantioselective route, and the structures of all key intermediates and the natural product itself are unequivocally confirmed through X-ray crystallographic analysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Francisco Gaspar, Guilherme S. Caleffi, Paulo C. T. Costa-Junior, Paulo R. R. Costa
Summary: The Noyori-Ikariya Ru-II complexes were utilized to promote the reduction of C=C/C=O bonds in isoflavones, leading to selective formation of cis-3-phenylchroman-4-ols with different substituents at the 2' position of the B-ring in high yields and excellent enantioselectivities. New synthetic strategies for obtaining enantioenriched isoflavanones and pterocarpans were also demonstrated in this study, showcasing the versatility of the developed method.
Article
Chemistry, Multidisciplinary
Marko Nesic, David B. Ryffel, Jonathan Maturano, Michael Shevlin, Scott R. Pollack, Donald R. Gauthier Jr, Pablo Trigo-Mourin, Li-Kang Zhang, Danielle M. Schultz, Jamie M. McCabe Dunn, Louis-Charles Campeau, Niki R. Patel, David A. Petrone, David Sarlah
Summary: The collaborative total synthesis of darobactin A, a selective antibiotic against Gram-negative bacteria, has been achieved in a convergent manner using D-Garner's aldehyde and L-serine as starting materials. The synthesis involved 16 steps and three scalable routes were developed to synthesize non-canonical amino acids. The closure of the bismacrocycle was successfully achieved through sequential, halogen-selective Larock indole syntheses, with the cyclization order playing a crucial role in the formation of the desired atropisomer.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Lucas Bacheley, Ricardo Molina Betancourt, Rathies Ravindra, Gerard Guillamot, Phannarath Phansavath, Virginie Ratovelomanana-Vidal
Summary: A straightforward method for synthesizing novel families of enantioenriched cis-monofluorinated carbocyclic alcohols has been developed using ATH/DKR. The reaction exhibited high yields (up to 97%), high diastereoselectivity (up to 99:1 dr), and high enantioselectivity (up to 97% ee). Additionally, trans-difluorinated indans, tetrahydronaphthalenes, tetrahydroquinolines, and chromans were synthesized via deoxofluorination of the corresponding cis-fluoro alcohols.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Daniel J. Tindall, Steffen Mader, Alois Kindler, Frank Rominger, A. Stephen K. Hashmi, Thomas Schaub
Summary: Sugar alcohols are important for the food industry and can be produced in large quantities with increased yield and stereoselectivity through a homogeneous system.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Pinke Yu, Danyi Chen, Yiwen Liu, Congcong Yin, Qixing Liu, Haifeng Zhou
Summary: An asymmetric transfer hydrogenation of 2-oxazolones using a chiral diamine ruthenium catalyst, potassium formate as a hydrogen source, potassium carbonate as an additive in 2,2,2-trifluoroethanol has been described. The reaction yielded a series of chiral 2-oxazolidinones with 29%-95% yields and 86%->99% ee's. Gram-scale synthesis and downstream derivatizations of chiral 2-oxazolidinone demonstrate the practicality of this method.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Liu-Yang Pu, Zhiyue Li, Limin Li, Yucui Ma, Shengquan Hu, Zhengzhi Wu
Summary: We report a concise asymmetric total synthesis of isopavine alkaloids, which possess a unique azabicyclo[3.2.2]nonane tetracyclic skeleton. The key steps involve iridium-catalyzed asymmetric hydrogenation of unsaturated carboxylic acids, Curtius rearrangement, and Eschweiler-Clarke methylation, achieving an enantioselective approach to isopavine alkaloids in 6-7 linear steps. Moreover, isopavine alkaloids, especially (-)-reframidine (3), are found to exhibit effective antiproliferative effects on various cancer cell lines for the first time.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Liu-Yang Pu, Zhiyue Li, Limin Li, Yucui Ma, Shengquan Hu, Zhengzhi Wu
Summary: In this study, we describe a concise and enantioselective total synthesis of isopavine alkaloids with a unique azabicyclo[3.2.2]nonane tetracyclic skeleton. Key steps include iridium-catalyzed asymmetric hydrogenation, Curtius rearrangement, and Eschweiler-Clarke methylation, enabling the synthesis of isopavine alkaloids in 6-7 linear steps. Additionally, we discovered that isopavine alkaloids, particularly (-)-reframidine (3), exhibit significant antiproliferative effects on various cancer cell lines for the first time.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Isaac D. Falk, Balint Gal, Ahanjit Bhattacharya, Jeremy H. Wei, Paula V. Welander, Steven G. Boxer, Noah Z. Burns
Summary: Archaeal glycerol dibiphytanyl glycerol tetraethers (GDGT) are unusual membrane lipids found in Archaea, including extremophiles. Interest in studying their biophysical properties and biosynthesis is high, but limited access to pure samples has hindered progress in this area. This study reports a concise synthesis method for archaeal tetraether lipid parallel GDGT-0 and derivatives with different polar groups for self-assembly.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Qixing Liu, Mengna Liu, Jinbiao Chen, Jinlong Wang, Haifeng Zhou
Summary: This paper describes a highly efficient transfer hydrogenation of alpha-aryl selenomethyl ketones using a readily available chiral diamine-derived ruthenium complex as a catalyst and a mixture of formic acid and triethylamine as a hydrogen source in dichloromethane under ambient conditions. A wide range of chiral beta-hydroxy selenides was obtained with 90-99% ee values and moderate to good yields. The practicality of the method was demonstrated through gram-scale synthesis and downstream derivatization.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Andrej Emanuel Cotman
Summary: Noyori-Ikariya-type ruthenium(II)-catalysts have been used for 25 years in asymmetric transfer hydrogenation for the synthesis of chiral secondary alcohols. Recent progress has been made in understanding the asymmetric reduction of complex ketones, controlling up to four stereocenters in a single transformation. Intriguing multi-chiral molecular architectures can be prepared via ATH for drug discovery.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Yuta Takeuchi, Kengo Akagawa, Kazuaki Kudo
Summary: Solid-phase biomimetic polyketide synthesis has been developed, which involves specific steps for carbon chain elongation and transformation to synthesize natural products, with monitoring and confirmation through colorimetric tests and NMR.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Bart Herle, Georg Spaeth, Lucas Schreyer, Alois Fuerstner
Summary: This study demonstrates a novel approach to synthesizing a large estate of 16-membered macrolide antibiotics using a unified method. Key building blocks were prepared through an asymmetric vinylogous Mukaiyama aldol reaction, leading to the creation of two structurally distinct series of antibiotic targets. Notable late-stage maneuvers included rare catalytic reactions and the underutilized possibility of forging complex macrolactone rings.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Ruben L. H. Andringa, Niels A. W. Kok, Arnold J. M. Driessen, Adriaan J. Minnaard
Summary: Ir-catalyzed asymmetric alkene hydrogenation combined with an established C-13-NMR method can effectively synthesize saturated isoprenoids and mycoketides, significantly improving synthetic efficiency.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.