Article
Chemistry, Multidisciplinary
Zhi-Peng Bao, Xiao-Feng Wu
Summary: This article develops an efficient and convenient palladium-catalyzed carbonylation reaction for the synthesis of 2-cyano-N-acetamide and 2-cyanoacetate compounds. The reaction proceeds under mild conditions via a radical intermediate, suitable for late-stage functionalization. Gram-scale experiment was successfully performed with low catalyst loading, yielding the target product excellently. Additionally, this transformation can be carried out under atmospheric pressure and provides alternative routes to drug precursors.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Atsushi Umehara, Soma Shimizu, Makoto Sasaki
Summary: This report presents a practical and operationally simple method for the direct N-acylation of less nucleophilic heterocycles and amides with carboxylic acids. The method utilizes the DMAPO/Boc(2)O system and does not require pre-activation of substrates. It demonstrates high yield, excellent functional group tolerance, and broad substrate scope, making it suitable for both academic and industrial laboratories.
Article
Chemistry, Multidisciplinary
Can-Can Bao, Hui-Zhen Du, Yan-Long Luo, Bing-Tao Guan
Summary: A method of direct alkylation of benzamides with methyl sulfides promoted by the base LDA has been reported, successfully achieving an efficient and selective synthesis of alpha-sulfenylated ketones.
COMMUNICATIONS CHEMISTRY
(2021)
Article
Chemistry, Applied
Atsushi Umehara, Soma Shimizu, Makoto Sasaki
Summary: This report presents a general method for the direct N-acylation of N-heterocycles using the DMAPO/Boc(2)O system. This one-pot method allows for the synthesis of bulky N-acyl heterocycles from less nucleophilic N-heterocycles and sterically hindered carboxylic acids. The protocol has also been successfully applied to the one-pot N-acylation of 7-azaindoles.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Ryo Inoue, Momoka Yokoyama, Itsuki Maruyama, Yasuhiro Morisaki
Summary: Since the development of the first porphyrin synthesis method in 1935, porphyrin derivatives have played a crucial role in chemical sciences. Most synthetic routes involve oxidative aromatization. In this study, we propose a one-pot reaction method to synthesize ABCD-porphyrins, both chiral and achiral, using a platinum complex as a template for coordination, cyclization, and dehydrative aromatization. This procedure allows the synthesis of ABCD-porphyrin Pt(II) complexes from corresponding dipyrrinatoPt(II) complexes and bisformyldipyrrins. The ability to construct a C1-symmetrical ABCD-porphyrin with intrinsic chirality from achiral precursors is also demonstrated. The photophysical properties of the obtained molecules are also described in detail.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Patrick S. Fier, Riley A. Roberts, Reed T. Larson
Summary: We have developed a method for converting esters to ketones in a single step using simple reagents. This selective transformation is achieved by activating the adjacent carbon to deprotonation through the use of a transient sulfinate group on the nucleophile, allowing the formation of a carbanion that adds to the ester. This reaction is then followed by another deprotonation step to prevent further addition, and the resulting dianion spontaneously fragments the SO2 group upon quenching with water to produce the ketone product.
Article
Chemistry, Organic
Majid Ahmad Ganie, Faheem Fayaz, Muneer-ul-Shafi Bhat, Masood Ahmad Rizvi, Shabnam Raheem, Bhahwal Ali Shah
Summary: A mild approach for the synthesis of N-acyl-N,O-hemiacetals has been reported, utilizing an electron donor-acceptor complex. This protocol allows for direct access to electrophilic N-acylimines at room temperature without prefunctionalization of the hydroxyl group. The in situ generated N-acylimine reacts with different nucleophiles to yield diverse scaffolds.
Article
Chemistry, Applied
Wanying Yan, Zhonghua Qu, Feng Zhao, Guo-Jun Deng, Guo-Jiang Mao, Huawen Huang
Summary: A mild visible-light induced 4CzIPN/H+ photoredox system was developed for the formal C-O bond cleavage of hydroxyketones, serving as a carbon radical precursor. This process was successfully applied in the coupling/cyclization reaction of N-arylacrylamides, providing a practical access to acyl oxindoles. The protocol offers advantages such as no need for any metal catalyst and additive, high yield, broad substrate scope, gram scalability, and sole byproduct release of H2O.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Shuting Zhong, Xianfu Fang, Yiting Wang, Gong Zhang, Yangfeng Li, Yizhou Li
Summary: In this study, a new method for on-DNA synthesis of diverse C3-functionalized indole derivatives is presented, enabling indole-based diversification in the construction of chemical libraries.
Article
Chemistry, Multidisciplinary
Jiahua Chen, Jun Wei Lim, Derek Yiren Ong, Shunsuke Chiba
Summary: The synthesis of alpha-tertiary amines was achieved by iteratively adding carbon nucleophiles to N,N-dialkyl carboxamides, forming anionic tetrahedral carbinolamine intermediates. These intermediates were then treated with bromotrimethylsilane followed by organomagnesium or organolithium reagents to produce alpha-tertiary amines. The use of (trimethylsilyl)methylmagnesium bromide as the second nucleophile allowed for aza-Peterson olefination, resulting in the formation of 1,1-diarylethylenes after acidic work-up.
Article
Chemistry, Multidisciplinary
William I. Nicholson, Fabien Barreteau, Jamie A. Leitch, Riley Payne, Ian Priestley, Edouard Godineau, Claudio Battilocchio, Duncan L. Browne
Summary: The direct mechanochemical amidation of esters by ball milling is a simple and efficient method for preparing a diverse library of amide structures. This method is specifically effective for heteroaromatic and heterocyclic components. It has been successfully applied to the synthesis of active pharmaceutical ingredients and agrochemicals, as well as gram-scale synthesis of active pharmaceuticals without the need for a reaction solvent.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Cristiana Margarita, Davide Di Francesco, Helena Lundberg
Summary: Zirconocene triflate is a potent catalyst that can activate C-O bonds in carboxylic acids and alcohols without the need for water scavenging techniques. This article provides an overview of its use in direct amidation, esterification, and etherification reactions, as well as a discussion on the mechanistic aspects and catalyst class.
Article
Chemistry, Multidisciplinary
Jing Qi, Xiyan Wang, Gan Wang, Srinivas Reddy Dubbaka, Patrick ONeill, Hwee Ting Ang, Jie Wu
Summary: This study presents a green and environmentally friendly approach for the synthesis of imides using electrocatalytic oxidation with H2O as the oxygen source. The method eliminates the need for toxic or expensive oxidants and achieves high yields under mild reaction conditions. It shows broad substrate compatibility and potential for industrial applications.
Article
Chemistry, Organic
Huicong Xing, Meijuan Chen, Dong Zhang, Zhishuai Geng, Peizhong Xie, Teck-Peng Loh
Summary: A transition-metal-free catalytic system was developed for the dehydrative cross-coupling of unactivated primary/secondary alcohols with amines/amides, achieving the cleavage of C-OH bond and formation of C-N bond under environmentally benign conditions.
Article
Chemistry, Physical
Floriane Doche, Thomas Poisson, Tatiana Besset
Summary: A photocatalytic method for C(sp(3))-H trifluoromethylthiolation of amides has been developed, which tolerates a wide range of functional groups and allows the functionalization of aromatic and aliphatic amides in high yields using a low catalytic loading of an organophotocatalyst. This approach enables the synthesis of original fluorinated acyclic thioaminals.
