Article
Chemistry, Organic
Amr Elagamy, Ismail Althagafi, Ramendra Pratap
Summary: A mild and effective method for synthesizing conjugated trienes was developed via nitroethane-mediated ring contraction and decarboxylative rearrangement of spirobutenolides and butenolides. The (E)-isomer of trienes could be obtained from 2-oxobenzo[h]chromenes using step-wise or one-pot approaches. New substrates, such as butenolides 4a-l, were utilized for triene construction. The mixture of spirobutenolide isomers yielded the (E)-isomer of trienes, while butenolide isomer reactions produced a mixture of triene isomers in different ratios.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Lisi Yuan, Ya Fang, Zhaobo Zhou, Tinghong Lv, Yingpeng Su, Jian Liu, Xiaolei Wang
Summary: This Letter describes a highly diastereoselective synthesis method for C-hydroxymethine glycosides from glycal anomers using an achiral N-heterocyclic carbene-copper catalyst. The diastereoselectivity is controlled by both the stereocenter of the substrate and the chirality of the N-heterocyclic carbene-copper complex, independent of the stereochemistry of C5 and the anomeric position. This approach allows for the production of a diverse range of C-hydroxymethine glycosides using versatile glycals and various functionalized aldehydes.
Article
Chemistry, Applied
Eric Sirota, Thomas Kwok, Richard J. Varsolona, Aaron Whittaker, Teresa Andreani, Scott Quirie, Eric Margelefsky, David J. Lamberto
Summary: Islatravir, a potent nucleoside reverse transcriptase translocation inhibitor, is purified using two robust crystallization methods to control particle size distribution and impurity profile.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2021)
Article
Chemistry, Organic
Eilidh G. Young, Phillip S. Grant, Daniel P. Furkert, Margaret A. Brimble
Summary: Lycibarbarines A-C are spirocyclic alkaloids with a unique tetracyclic framework. The first total syntheses of lycibarbarines A-C were achieved over 10 steps. The spiroketal unit of lycibarbarines A-C exhibits unusually high resistance to acid-mediated isomerization and epimerization.
Article
Chemistry, Applied
Sumei Ren, Mark A. Huffman, Aaron M. Whittaker, Hao Yang, Christopher C. Nawrat, David J. Waterhouse, Kevin M. Maloney, Neil A. Strotman
Summary: The synthesis of the carbon-14-labeled unnatural nucleoside islatravir, an investigational HIV drug, was achieved through a one-pot biocatalytic cascade starting from acetaldehyde-2-C-14. Combining enzymatic reactions into multistep biocatalytic cascades not only accelerates delivery and increases the yield, but also eliminates handling of radioactive intermediates and minimizes radioactive waste.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2021)
Article
Biochemistry & Molecular Biology
Xueying You, Yifei Cai, Chenyu Xiao, Lijuan Ma, Yong Wei, Tianpeng Xie, Lei Chen, Hui Yao
Summary: An effective and direct methodology using AgOTf as a catalyst has been developed for the stereoselective synthesis of alpha-2-deoxythioglycosides. This method not only allows the synthesis of disaccharides, but also enables successful late-stage glycosylation of estrogen, L-menthol, and zingerone with thiol compounds.
Article
Chemistry, Physical
Theo Magrino, Fabio Pietrucci, A. Marco Saitta
Summary: This study provides a quantitative microscopic description of the complex Strecker reaction by adopting a state-of-the-art ab initio computational approach. It reveals the step-by-step chemical pathway from Strecker precursors to glycine in solution and calculates the corresponding full free energy landscape, demonstrating agreement with experimental data and providing new insights into this crucial bottleneck for the emergence of life.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Freya Taday, Ryan Cairns, Adam O'Connell, Elaine O'Reilly
Summary: A hybrid bio-organocatalytic cascade method was developed for the synthesis of 2-substituted piperidines, utilizing a transaminase to generate a key reactive intermediate for the Mannich reaction.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Dhiman Saha, Gour Hari Mandal, Rajib Kumar Goswami
Summary: A convergent route has been developed for the asymmetric total synthesis of potent anticancer polyketide natural product amphirionin-2, with key features including Sharpless asymmetric dihydroxylation, cycloetherification, Wittig olefination, Julia-Kocienski olefination, and Crimmins propionate aldol reaction after the proposed structures of amphirionin-2 were revised based on a recent report.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Kanokwan Jaithum, Jumreang Tummatorn, Bundet Boekfa, Charnsak Thongsornkleeb, Kittipong Chainok, Somsak Ruchirawat
Summary: A method using a silver catalyst and acid for the diastereoselective synthesis of spirocyclic ethers has been developed, showing good yields of 97% and broad substrate applicability. The proposed reaction mechanisms and stereoselectivity outcomes have been investigated using DFT calculation.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Daiki Tomon, Satoru Arimitsu
Summary: The acetyl group of chiral α-fluorinated dicarbonyl compounds was converted to nonaflates through a reaction with perfluorobutanesulfonyl fluoride in the presence of DBU, with yields ranging from 82% to 95%. These nonaflates were used in Suzuki and Sonogashira coupling reactions to produce chiral tertiary allylic fluorides with gem-disubstituted terminal alkenes and excellent optical purities (45-91%, ≥94% ee). Additionally, chiral tertiary propargylic fluorides were obtained from the reaction of nonaflates with DBU (73-86%, ≥94% ee).
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
David A. Candito, Yingchun Ye, Ryan Quiroz, Michael H. Reutershan, David Witter, Surendra B. Gadamsetty, Hongming Li, Josep Sauri, Sebastian E. Schneider, Yu-hong Lam, Rachel L. Palte
Summary: This study presents a flexible and robust strategy for accessing tetrahydrofuro[3,4-b]furan nucleoside analogues in the context of a PRMT5 inhibitor program. Compound 1.1-C was synthesized and demonstrated to be a potent PRMT5 inhibitor, laying the groundwork for the development of new inhibitors and nucleoside chemical matter for drug discovery programs.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Yuta Miyamoto, Arihiro Iwasaki, Haruka Fujimura, Chihiro Kudo, Naoaki Kurisawa, Osamu Ohno, Kiyotake Suenaga
Summary: Caldorazole, a novel polyketide, was isolated from a marine cyanobacterium in 2022. Despite lacking chiral centers, it exhibits potent inhibitory activity against mitochondrial respiratory chain complex I. To study its structure-activity relationship, we accomplished the first total synthesis of caldorazole using a convergent synthetic route, aiming to establish a method for obtaining caldorazole without relying on biological resources.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Runze Mao, Daniel J. J. Wackelin, Cooper S. S. Jamieson, Torben Rogge, Shilong Gao, Anuvab Das, Doris Mia Taylor, K. N. Houk, Frances H. H. Arnold
Summary: By engineering bacterial cytochrome P450, chiral 1,2,3-polysubstituted cyclopropanes can be synthesized regardless of the stereopurity of the olefin substrates used. This new method simplifies the synthesis of chiral cyclopropanes and expands the application of classical cyclopropanation methods.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Ren Zou, Weijin Zhang, Min Dai, Gangtie Lei, Qike Jiang, Hujun Cao, Ping Chen
Summary: A simple and efficient organic solvent-assisted ball-milling process was developed to synthesize magnesium and lithium nanoparticles. Acetone was found to react with magnesium, forming metastable magnesium complexes that significantly altered the properties of the nanoparticles. This method provides a new strategy for synthesizing light metal nanoparticles.
