Editorial Material
Chemistry, Multidisciplinary
Fredrik Cederbaum, Daniele Choueiry, C. Coperet, Sebastien Gagneur, Frederic Lamaty, Estelle Metay, Jean-Luc Montchamp, Christophe Rousset
Summary: Ei-ichi Negishi is known for his pioneering work in transition-metal catalyzed reactions in organic synthesis, and for his kindness and generosity in both the scientific community and in life.
Review
Chemistry, Multidisciplinary
You Wang, Yuli He, Shaolin Zhu
Summary: Migratory cross-coupling via metal migration is a significant process in academic and industrial fields, providing an attractive alternative for the synthesis of challenging structures. This Account outlines recent progress and developments in the field, including migration-functionalization modes, diverse functionalizations, and strategies for regio- and stereocontrol.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Organic
Qian Tu, Zheyuan Wang, Zhongchao Zhang, Jun Huang, Zhen Yang
Summary: The structurally intriguing tetracyclic core of complex harziane diterpenoid was successfully constructed in 14 steps from commercially available compound. Key methods used include Mn/Cu-mediated oxidative 1,3-dicarbonyl radical cascade cyclization reaction and Au-catalyzed diastereoselective formal [2 + 2] cycloaddition.
Article
Chemistry, Organic
Jeymy T. Sarmiento, Maria Carcel, Carmen Ramirez de Arellano, Teresa Varea, Gregorio Asensio, Andrea Olmos
Summary: In this study, alpha-chloromethylketimines have been synthesized through a gold-catalyzed hydroamination reaction of aromatic and aliphatic 1-chloroalkynes with aromatic amines. This method allows the preparation and spectroscopic characterization of alpha-chloromethylketimines with high purity, complete conversion, and atom economy. The synthetic usefulness of this methodology has been demonstrated through the preparation of beta-chloroamines and indoles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jeymy T. T. Sarmiento, Maria Carcel, Carmen Ramirez de Arellano, Teresa Varea, Gregorio Asensio, Andrea Olmos
Summary: α-Chloromethylketimines have been synthesized through a gold-catalyzed hydroamination reaction of aromatic amines with aromatic and aliphatic 1-chloroalkynes. This method allows for the preparation and spectroscopic characterization of α-chloromethylketimines, as well as the synthesis of β-chloroamines and indoles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Zhengfen Liu, Chao Li, Jian Chen, Xiaobo Li, Fumang Luo, Feixiang Cheng, Jian-Jun Liu
Summary: The integration of photoactive units into metal-organic frameworks (MOFs) is an area of interest for enhancing properties such as photomagnetism, photoconductivity, and photocatalysis. A novel photoactive MOF based on a perylenediimide derivative has been successfully synthesized, demonstrating efficient electron-transfer photocatalytic capabilities for reactions with alkenes and amines. This photocatalyst offers high efficiency, low catalyst loading, and ease of synthesis, making it a practical option for various applications.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Pan Zhou, Yuqiang Li, Tao Xu
Summary: A novel molybdenum-oxo-complex-catalyzed intermolecular cross-coupling of benzyl alcohols has been reported, which can efficiently handle various types of alcohol substrates and tolerate many functional groups sensitive to low-valent transition metals.
Review
Chemistry, Organic
Li Sida, Shu Xing-Zhong, Wu Lipeng
Summary: The transition metal-catalyzed hydroboration of alkenes and alkynes, especially with late-transition metals, is highly efficient in the production of boronate esters. However, the use of early-transition metals such as zirconium and titanium is limited. This review summarizes the development of zirconium and titanium mediated hydroboration of alkenes and alkynes, and discusses the research trends in this area.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Andrei A. . Leushukou, Anastasiya V. Krech, Alaksiej L. Hurski
Summary: In this study, a photocatalyst-free nickel-catalyzed cross-coupling reaction was reported, which achieved efficient alkylation of various organic halides using alkyltitanium alkoxides generated in situ from Grignard reagents and Ti(OiPr)(4) upon irradiation with blue light.
Article
Chemistry, Organic
Bin Li, Jiang-Ling Shi, Ying Xia
Summary: The construction of all-carbon quaternary centers in small-ring systems is an important yet challenging task in organic synthesis. In this study, we developed a practical method for building all-carbon quaternary centers in gem-difluorinated cyclopropanes (DFCs) by utilizing gem-difluorocyclopropyl bromides (DFCBs) as general and versatile building blocks. The reaction involves the participation of a gem-difluorocyclopropyl radical intermediate, which undergoes coupling with a wide range of nucleophiles under copper catalysis.
Article
Chemistry, Organic
Bin Li, Jiang-Ling Shi, Ying Xia
Summary: In this study, a practical method for building all-carbon quaternary centers in gem-difluorinated cyclopropanes was developed using gem-difluorocyclopropyl bromides as a general building block. The reaction involves the participation of a gem-difluorocyclopropyl radical intermediate, which can undergo coupling with a wide range of nucleophiles under copper catalysis.
Article
Chemistry, Multidisciplinary
Yanling Shen, Ning Lei, Cong Lu, Dailin Xi, Xinxin Geng, Pan Tao, Zhishan Su, Ke Zheng
Summary: A visible-light-induced modular methodology was reported for the synthesis of complex 3,3'-disubstituted oxindole derivatives, showing high functional group tolerance and broad substrate compatibility. The strategy enables modular modification of complex drug-like compounds in one chemical step.
Article
Multidisciplinary Sciences
Xianqing Wu, Chenglong Wang, Ning Liu, Jingping Qu, Yifeng Chen
Summary: Carbonylative reactions with CO gas are crucial in organic synthesis. In this study, the authors demonstrate a three-component tandem acylzincation/cyclization reaction using an earth-abundant nickel catalyst and 1 atm of CO gas under mild conditions.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Jun Chen, Yu-Jie Liang, Peng-Zi Wang, Guo-Qing Li, Bin Zhang, Hao Qian, Xiao-Die Huan, Wei Guan, Wen-Jing Xiao, Jia-Rong Chen
Summary: This study presents a photoinduced copper-catalyzed cross-coupling reaction for the generation of allylic esters. The reaction proceeds at room temperature with high regio- and enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Yuyang Bai, Liping Cao, Siyuan Li, Guang'an Zhang, Yingguo Liu, Fengqian Zhao, Junliang Wu
Summary: A photoredox/Lewis acid cooperative catalytic system has been developed for the construction of C-vinyl-C-Rf bonds through the dehydrative difluoroalkylation of benzyl alcohols. Various allylic gem-difluorides were obtained with moderate yields and good to excellent E/Z selectivity. Control experiments were conducted and a possible mechanism for this process was proposed.
Article
Chemistry, Organic
HtooTint Wai, Kang Du, Jason Anesini, Wan Shin Kim, Alan Eastman, Glenn C. Micalizio
Article
Chemistry, Organic
Kang Du, Matthew J. Kier, Arnold L. Rheingold, Glenn C. Micalizio
Article
Chemistry, Organic
Adam B. Millham, Matthew J. Kier, Robert M. Leon, Rajdip Karmakar, Zachary D. Stempel, Glenn C. Micalizio
Article
Chemistry, Organic
Robert M. Leon, Divya Ravi, Jennifer S. An, Carmen L. del Genio, Arnold L. Rheingold, Arti B. Gaur, Glenn C. Micalizio
Article
Chemistry, Organic
Rajdip Karmakar, Arnold L. Rheingold, Glenn C. Micalizio
Article
Multidisciplinary Sciences
Wan Shin Kim, Zachary A. Shalit, Sidney M. Nguyen, Emmalie Schoepke, Alan Eastman, Thomas P. Burris, Arti B. Gaur, Glenn C. Micalizio
NATURE COMMUNICATIONS
(2019)
Article
Chemistry, Multidisciplinary
Kang Du, Matthew J. Kier, Zachary D. Stempel, Valer Jeso, Arnold L. Rheingold, Glenn C. Micalizio
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Organic
Adam B. Millham, Chinmay P. Bhatt, Glenn C. Micalizio
Article
Chemistry, Organic
Zachary A. Shalit, Lucas C. Valdes, Wan Shin Kim, Glenn C. Micalizio
Summary: The total synthesis of (+)-03219A, a rare Delta(8,9)-pregnene isolated from marine-derived Streptomyces sp. SCSIO 03219, involved a series of transformations from epichlorohydrin to an ent-estrane, then to a nat-androstane, ultimately establishing the natural product target. The success of these studies relied on the implementation of two rearrangement processes to formally invert the quaternary center at C13 and establish the C10 quaternary center.
Article
Chemistry, Medicinal
Lauren E. Markham, Jessica D. Tolbert, F. Jon Kull, Charles R. Midgett, Glenn C. Micalizio
Summary: The chiral conformation of palmitoleic acid when bound to the bacterial pathogen Vibrio cholerae's virulence genes master regulator ToxT served as inspiration for designing a novel class of fatty acid mimetics. The best mimetic, based on a chiral hydrindane, was discovered to be a potent inhibitor of the target. Synthetic chemistry utilizing stereoselective annulative cross-coupling reactions and dissolving metal reduction was crucial in establishing the C13 and C9 stereocenters for these studies.
ACS MEDICINAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Organic
Joshua M. Nicholson, Adam B. Millham, Andrea R. Bucknam, Lauren E. Markham, Xenia Ivanna Sailors, Glenn C. Micalizio
Summary: Tetracyclic terpenoid-derived natural products are a diverse class of medically relevant compounds. A four-stage synthetic strategy has been developed to access unique stereodefined systems of these compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Andrea R. Bucknam, Glenn C. Micalizio
Summary: The asymmetric de novo synthesis of octanorcucurbitacin B, a cucurbitane natural product, was achieved using a novel approach. This approach bypassed the traditional biosynthetic hypothesis and directly accessed the cucurbitane skeleton. The synthesis involved a sequence of reactions, ultimately resulting in the conversion to octanorcucurbitacin B.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
HtooTint Wai, Thomas Koelblen, Matthew E. Hayes, Thomas P. Burris, Glenn C. Micalizio
Summary: Progress has been made in the asymmetric synthesis of euphanes, and a C14-desmethyl euphane system with five differentially substituted and electronically distinct alkenes has been successfully prepared. The route employed involves sequential metallacycle-mediated annulative cross-coupling, double asymmetric Bronsted acid mediated intramolecular Friedel-Crafts alkylation, and an oxidative rearrangement to establish the required C10 quaternary center. These studies have also led to the discovery of a novel euphane-based modulator of the Liver X Receptor.
Article
Chemistry, Organic
Adam B. Millham, Glenn C. Micalizio
Summary: Efforts have been made to introduce C17 beta-substitution by late-stage functionalization of stereodefined steroidal D-ring vinylepoxides in a program aiming to establish a common sequence of C-C bond-forming reactions for asymmetric construction of tetracyclic triterpenoid natural products and related synthetic systems. Cyanocuprates were found to participate in syn-S(N)2' reactions resulting in products with various C17 beta-substituents and a beta-OH at C14.
Article
Chemistry, Organic
Zachary A. Shalit, Glenn C. Micalizio