Article
Chemistry, Multidisciplinary
Quentin Dherbassy, Srimanta Manna, Chunling Shi, Watcharapon Prasitwatcharakorn, Giacomo E. M. Crisenza, Gregory J. P. Perry, David J. Procter
Summary: In this study, an enantioselective copper-catalyzed borylative cyclization was reported for the assembly of privileged pyrroloquinazolinone motifs. The reaction demonstrated high enantio- and diastereocontrol, yielding products with quaternary stereocenters. The utility of the products was further demonstrated through additional manipulations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Thao T. Nguyen, Khang X. Nguyen, Phuc H. Pham, Duc Ly, Duyen K. Nguyen, Khoa D. Nguyen, Tung T. Nguyen, Nam T. S. Phan
Summary: This study reports a new method for the synthesis of pyrido-fused quinazolinones via copper-catalyzed cascade reactions, which shows a broad substrate scope and good tolerance of functional groups. The method allows the synthesis of complex heterocyclic structures in a single step, serving as a valuable complement to existing synthetic protocols.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Li Pang, Shu-Jun Fang, Pei-Sen Zou, Wang Wang, Jun-Cheng Su, Xiao-Qing Liu, Cheng-Xue Pan, Dong-Liang Mo, Gui-Fa Su
Summary: We report a transition-metal free [4 + 4] cycloaddition reaction between 2-alkynyl quinazolines and aza-ortho-quinone methides (ao-QMs) generated from 2-(bromomethyl)anilines, leading to the synthesis of various [1,5]diazocino[2,1-b]quinazolinones in good to excellent yields under mild reaction conditions and short reaction time. Furthermore, a [1,5]diazocino[2,1-b]quinazolinone derived from estrone was easily prepared in 30% total yield over five steps, and showed significant inhibition of nitric oxide generation in LPS-stimulated RAW264.7 cells. This method offers advantages such as broad substrate scope, gram-scale preparation, and simple purification operation without flash column chromatography.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Subrata Sahoo, Shantanu Pal
Summary: A novel and efficient method for synthesizing quinazolinones via copper-catalyzed one-pot synthesis has been developed using urea, hydrazine hydrate, and atmospheric oxygen as reagents, showing good adaptability and a wide range of substrates.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Bin Sun, Panyi Huang, Zhiyang Yan, Xiayue Shi, Xiaoli Tang, Jin Yang, Can Jin
Summary: A novel visible-light-induced radical tandem tri-fluoromethylation/cyclization reaction of unactivated alkenes with sodium perfluoroalkanesulfinates has been developed, leading to perfluoroalkyl-substituted quinazoline alkaloids. Remarkably, this transformation can be carried out without the use of any metal catalyst, strong oxidant, or external photosensitizer.
Article
Chemistry, Organic
Chenghao Li, Shuxin Zhang, Shan Li, Yu Feng, Qing-Hua Fan
Summary: An efficient Ru-catalyzed enantioselective hydrogenation method has been successfully developed for the synthesis of chiral dihydroquinoxalinones and dihydroquinazolinones with excellent results (89-98% yields, up to 98% ee). Additionally, a key enantiopure dihydroquinoxalinone intermediate towards the synthesis of a bioactive BRD4 inhibitor was conveniently synthesized using this catalytic hydrogenation methodology.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Physical
Neda Salarinejad, Minoo Dabiri, Siyavash Kazemi Movahed
Summary: Pd/N-RGO nanohybrid was used as a catalyst for efficient C-H acyloxylation and halogenation reactions. The introduction of nitrogen into the graphene lattice enhanced the catalytic activities of palladium, and the catalyst showed no significant palladium leaching, allowing for its successful recovery and reuse without any noticeable decrease in catalytic activity.
COLLOID AND INTERFACE SCIENCE COMMUNICATIONS
(2022)
Review
Biochemistry & Molecular Biology
Martin Sweeney, Darren Conboy, Styliana I. Mirallai, Fawaz Aldabbagh
Summary: This review article provides a perspective on the synthesis of alicyclic and heterocyclic ring-fused benzimidazoles, imidazo[4,5-f]benzimidazoles, and imidazo[5,4-f]benzimidazoles. The synthesis methods are categorized and detailed, including various cyclization reactions and mechanisms. The biological activities and antitumor properties of these heterocycles are also discussed in the article.
Article
Chemistry, Physical
Dan Wen, Xing Ge, Ren-Guan Miao, Xinxin Qi, Xiao-Feng Wu
Summary: A palladium-catalyzed carbonylative synthesis of carboxamide substituted 2-pynones from methyl enynoates and nitroarenes has been developed. A wide range of carboxamide substituted 2-pynones were obtained in moderate to high yields with quite high functional group compatibility using nitroarenes as the nitrogen sources and Mo(CO)6 as both CO surrogate and reductant. Late-stage modifications of natural molecules were also achieved.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Mengfu Dai, Zhimin Sun, Liang-An Chen
Summary: This study reports a catalyst-controlled, tunable, and predictable regiodivergency in transforming internal aliphatic propargyl esters into diverse products, allowing facile access to regioisomers with high regio- and stereoselectivity. This method is important for the structural diversification of bioactive molecules, enabling the rapid assembly of structural analogs of pharmaceutical candidates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Kuruva Balanna, Soumen Barik, Shilpa Barik, Sayan Shee, Niket Manoj, Rajesh G. Gonnade, Akkattu T. Biju
Summary: While the selective synthesis of biaryls with axially chiral C-C bonds is well-known, the synthesis of compounds containing axially chiral C-N bonds is less explored, and the construction of axially chiral N-N bonds has received little attention. This study demonstrates the selective amidation reaction catalyzed by N-heterocyclic carbenes (NHCs), leading to the atroposelective synthesis of N-N axially chiral 3-amino quinazolinones. The NHC-catalyzed reaction of quinazolinones with a free N-H group and α,β-unsaturated aldehydes under oxidative conditions provides the atropisomeric quinazolinone derivatives under mild conditions and with a broad scope. Preliminary studies on experimental and density functional theory-based determination of N-N rotational barrier are also presented.
Article
Multidisciplinary Sciences
Ge Zhang, Yi-Kang Song, Fang Zhang, Ze-Jian Xue, Meng-Yao Li, Gui-Shan Zhang, Bin-Bin Zhu, Jing Wei, Chunsen Li, Chen-Guo Feng, Guo-Qiang Lin
Summary: The authors present a palladium-catalyzed cross-coupling reaction involving a beta-vinylic hydrogen elimination from an allylic palladium intermediate.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Yetong Zhang, Wenzhang Xiong, Lepeng Chen, Yinlin Shao, Renhao Li, Zhongyan Chen, Jingyuan Ge, Ningning Lv, Jiuxi Chen
Summary: This study presents a novel one-pot palladium-catalyzed method for synthesizing pyrazino-fused quinazolinones, with moderate to excellent yields in water. The resulting molecules exhibit tunable fluorescence, with some displaying aggregation induced emission properties, showing potential for applications in chemistry, biology, and materials science.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Applied
Yamini, Saurabh Sharma, Pralay Das
Summary: Substituted 2-alkyl-benzimidazoles were synthesized using polystyrene supported rhodium (Rh@PS) nanoparticles as catalyst, with good yields achieved through oxidation of alkylamines, transamination, and oxidative cyclisation. The process has a broad substrate scope, tolerance to various functional groups, and can be recycled up to four cycles without significant loss in catalytic activity.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Manoela Sacramento, Luis Pedro A. Piuma, Jose Edmilson R. Nascimento, Roberta Cargnelutti, Raquel G. Jacob, Eder Joao Lenardao, Diego Alves
Summary: In this study, two different compounds were successfully synthesized through a copper-catalyzed three-component reaction. The temperature and amount of Et3N used in the reactions have significant effects on the structure and yield of the products.
Article
Chemistry, Organic
Charlotte S. Richards-Taylor, Michael C. Willis
Summary: A synthetic route to benzosultams was reported, using palladium-catalysed aminsulfonylation of alkenyl iodides as the initial step, followed by an intramolecular transformation to form benzosultams. The method allows for good variation of starting alkenyl iodides and was shown to be more efficient than a related SNAr route.
Review
Chemistry, Multidisciplinary
Thomas Q. Davies, Michael C. Willis
Summary: Sulfinylamines, known for their reactivity as sulfur electrophiles and in Diels-Alder reactions, have been underutilized in organic synthesis in recent decades. Recent research has shown their potential in one-pot syntheses of sulfoximines and sulfonimidamides, highlighting their different reactivity modes and unappreciated potential.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Sangwon Seo, Ming Gao, Eva Paffenholz, Michael C. Willis
Summary: This study demonstrates that aryltriazenes can promote three distinctive types of C-H functionalization reactions, allowing the preparation of complex benzene molecules with diverse substitution patterns. The resulting products can undergo further derivatization providing traceless outcomes, providing a new method for the synthesis of complex organic molecules.
Article
Chemistry, Multidisciplinary
Xinlan A. F. Cook, Loic R. E. Pantaine, David C. Blakemore, Ian B. Moses, Neal W. Sach, Andre Shavnya, Michael C. Willis
Summary: Heteroaromatic sulfinates are effective nucleophilic reagents in Pd-0-catalyzed cross-coupling reactions with aryl halides. Base-activated, latent sulfinate reagents, such as beta-nitrile and beta-ester sulfones, have been introduced to address challenges in purifying and solubilizing metal sulfinate salts, as well as their tolerance to multi-step transformations. These latent sulfinate reagents have proven to be stable through multi-step substrate elaboration and amenable to scale-up processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Mingyan Ding, Ze-Xin Zhang, Thomas Q. Davies, Michael C. Willis
Summary: A new N-silyl sulfinylamine reagent has been developed for the rapid synthesis of a wide range of (hetero)aryl, alkenyl, and alkyl primary sulfinamides, which can be further converted to NH-sulfonimidamides. This two-step sequence is straightforward and provides a modular approach for the synthesis of NH-sulfonimidamides with flexibility in reaction components.
Review
Chemistry, Organic
Jonathan A. Andrews, Michael C. Willis
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Ndidi U. N. Iwumene, Daniel F. Moseley, Robert D. C. Pullin, Michael C. Willis
Summary: Rhodium-catalyzed hydroacylation reactions can be used to synthesize linear α,β-unsaturated enone intermediates, which can be used to construct diverse substituted saturated O-, N-, and S-heterocycles in a one-pot process. The reaction conditions can be adjusted to selectively form O-heterocycles with high levels of diastereoselectivity.
Review
Chemistry, Multidisciplinary
Terry Shing-Bong Lou, Michael C. Willis
Summary: The advent of sulfur(VI)-fluoride exchange (SuFEx) processes has led to research into electrophilic species featuring a sulfur-fluorine bond. Sulfonyl fluorides, known for their reactivity and stability, have been extensively studied for their applications in medicinal chemistry and chemical biology. Various synthetic approaches, starting from sulfur-containing and non-sulfur-containing substrates, have been developed. This review provides an overview of the challenges and progress in the synthesis and manipulation of sulfonyl fluorides.
NATURE REVIEWS CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Janette McKnight, Andre Shavnya, Neal W. Sach, David C. Blakemore, Ian B. Moses, Michael C. Willis
Summary: An efficient one-pot desulfinative cross-coupling reaction catalyzed by Pd is reported for the synthesis of medicinally relevant di(hetero)arylmethanes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Michael J. Tilby, Damien F. Dewez, Loic R. E. Pantaine, Adrian Hall, Carolina Martinez-Lamenca, Michael C. Willis
Summary: This study presents a late-stage functionalization strategy to convert sulfonamides into pivotal sulfonyl radical intermediates. The methodology utilizes a metal-free photocatalytic approach to access radical chemistry, enabling the combination of pharmaceutically relevant sulfonamides with an assortment of alkene fragments. The sulfinate anion can also be readily obtained, expanding the options for sulfonamide functionalization. Mechanistic studies indicate the involvement of energy-transfer catalysis (EnT).
Article
Chemistry, Multidisciplinary
Ze-Xin Zhang, Michael C. Willis
Summary: Sulfonamides, with their unique structure and properties, play a significant role in designing bioactive molecules. Mono aza variants, sulfonimidamides, and double aza analogs, sulfondiimidamides, are two functional groups. However, the synthesis of sulfondiimidamides is challenging, and their assembly and modification can be achieved through specific methods.
Article
Chemistry, Multidisciplinary
Ze-Xin Zhang, Charles Bell, Mingyan Ding, Michael C. Willis
Summary: Sulfondiimidamides, the double aza-variants of sulfonamides, are rarely reported due to their poor synthetic accessibility. In this study, a two-step synthesis of sulfondiimidamides was described, using a hypervalent iodine-mediated amination as the key step. The method demonstrated operational simplicity, broad scope, and concise nature, making it attractive for discovery chemistry applications.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Jonathan A. Andrews, Jagadeesh Kalepu, Christopher F. Palmer, Darren L. Poole, Kirsten E. Christensen, Michael C. Willis
Summary: This study presents a new method for the synthesis of sulfinamides, sulfonamides, and sulfonimidamides using readily available alkyl carboxylic acids as starting materials. The method utilizes acridine photocatalysts and light to generate alkyl radicals, which are then added to sulfinylamine reagents to obtain the desired products. The method is scalable, compatible with various functional groups, and can be used for the diversification of complex biologically active compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Michael J. Tilby, Damien F. Dewez, Adrian Hall, Carolina Martinez Lamenca, Michael C. Willis
Summary: In this study, the absolute configuration of sulfur-stereogenic aza-sulfur derivatives was determined using a unique feature of sulfonimidamides. Enantioselective alkylation was achieved by generating prochiral ions from sulfonimidamides with the help of a bis-quaternized phase-transfer catalyst. This demonstrates the potential of using configurationally labile aza-sulfur species in asymmetric catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Daniel F. Moseley, Jagadeesh Kalepu, Michael C. Willis
Summary: By using azine N-oxide substituted aldehydes, good reactivity and high effectiveness in intermolecular hydroacylation of alkynes can be achieved. The one-pot hydroacylation/deoxygenation sequence can convert the hydroacylation products to the corresponding azine.
