93961-29-6Relevant articles and documents
All-Carbon Tetrasubstituted Olefins Synthesis from Diazo Compounds and Iodonium Ylides under Blue LED Irradiation
Zhao, Yan-Rui,Li, Lei,Xu, Guo-Yong,Xuan, Jun
supporting information, p. 506 - 511 (2021/12/08)
A route for the construction of all-carbon tetra-substituted olefins through visible-light promoted coupling of diazo compounds with iodonium ylides was developed. A wide range of all-carbon tetra-substituted olefins was obtained in moderate to good yields. The synthetic values of the current method were further approved by the synthesis of natural isolates modified alkenes and the successful transformation of final olefins into important heterocycles. (Figure presented.).
B(C6F5)3-catalyzed O-H insertion reactions of diazoalkanes with phosphinic acids
Jiang, Jun,Zhang, Xinzhi,Zhang, Yangyang,Zhao, Jincheng
, p. 5772 - 5776 (2021/07/12)
A highly efficient base-, metal-, and oxidant-free catalytic O-H insertion reaction of diazoalkanes and phosphinic acids in the presence of B(C6F5)3has been developed. This powerful methodology provides a green approach towards the synthesis of a broad spectrum of α-phosphoryloxy carbonyl compounds with good to excellent yields (up to 99% yield). The protocol features the advantages of operational simplicity, high atom economy, practicality, easy scalability and environmental friendliness.
B(C6F5)3-Catalyzed site-selective N1-alkylation of benzotriazoles with diazoalkanes
Guo, Jing,Mandal, Dipendu,Stephan, Douglas W.,Wu, Yile,Zhao, Yunbo
, p. 7758 - 7761 (2021/08/13)
Alkylation of benzotriazoles is synthetically challenging, often leading to mixtures of N1 and N2 alkylation. Herein, metal-free catalytic site-selective N1-alkylation of benzotriazoles with diazoalkanes is described in the presence of 10 mol% of B(C6F5)3. These reactions provide N1-alkylated benzotriazoles in good to excellent yields and this protocol is successfully adapted to gram-scale syntheses as well as a derivative with antimicrobial activity.
Insertion of Diazo Esters into C-F Bonds toward Diastereoselective One-Carbon Elongation of Benzylic Fluorides: Unprecedented BF3Catalysis with C-F Bond Cleavage and Re-formation
Wang, Fei,Nishimoto, Yoshihiro,Yasuda, Makoto
, p. 20616 - 20621 (2021/11/23)
Selective transformation of C-F bonds remains a significant goal in organic chemistry, but C-F insertion of a one-carbon-atom unit has never been established. Herein we report the BF3-catalyzed formal insertion of diazo esters as one-carbon-atom sources into C-F bonds to accomplish one-carbon elongation of benzylic fluorides. A DFT calculation study revealed that the BF3 catalyst could contribute to both C-F bond cleavage and re-formation. This elongation provided α-fluoro-α,β-diaryl esters with a high level of diastereoselectivity. Various benzylic fluorides and diazo esters were applicable. The synthetic utility of this method was demonstrated by the synthesis of a fluoro analogue of a compound that is used as a transient receptor and potential canonical channel inhibitor.
Visible Light-Promoted Sulfoxonium Ylides Synthesis from Aryl Diazoacetates and Sulfoxides
Lu, Juan,Li, Lei,He, Xiang-Kui,Xu, Guo-Yong,Xuan, Jun
supporting information, p. 1646 - 1650 (2021/05/28)
A visible light-promoted reaction of donor/acceptor diazoalkanes with sulfoxides towards the synthesis of synthetically useful sulfoxonium ylides was reported. The reaction occurred under sole visible light irradiation without the need of any transition-metals or additives, affording the corresponding sulfoxonium ylides in moderate to good yields. The success of late-stage modification of natural isolates or drug candidates, scale-up reaction and transformation of sulfoxonium ylides to other useful molecules further rendered the approach valuable.
Borane Catalyzed Selective Diazo Cross-Coupling Towards Pyrazoles
Ariafard, Alireza,Babaahmadi, Rasool,Dasgupta, Ayan,Gierlichs, Lukas,Melen, Rebecca L.,Pahar, Sanjukta,Yates, Brian F.
, (2021/12/13)
Decomposition of donor-acceptor diazo compounds leads to the formation of reactive carbene intermediates. These can undergo a wide variety of carbene transfer reactions to yield synthetically useful products. Herein, we report a selective borane catalyzed cyclization reaction from the combination of two different diazo compounds to afford N-substituted pyrazoles. The selective decomposition of the more reactive α-aryl α-diazoester and subsequent reaction with a vinyl diazoacetate produces N-alkylated pyrazoles in a regioselective manner. Catalytic amounts of tris(pentafluorophenyl)borane (10 mol%) were employed to afford the pyrazole products (36 examples) in yields from 59 to 80%. Extensive DFT studies have been undertaken to interpret the mechanism for this reaction which was found to go through two tandem catalytic cycles, both catalyzed by B(C6F5)3.
Catalyst-free, scalable heterocyclic flow photocyclopropanation
Kl?pfer, Viktor,Eckl, Robert,Flo?, Johannes,Roth, Philippe M. C.,Reiser, Oliver,Barham, Joshua P.
supporting information, p. 6366 - 6372 (2021/09/10)
Industrial process development is driven by several factors, including safety, cost, robustness and environmental aspects. However, attempts to establish aryl diazo esters-which are highly valued in academic research for their reactivity as carbene precur
Engineering Dirhodium Artificial Metalloenzymes for Diazo Coupling Cascade Reactions**
Bultman, Max J.,Huang, Rui,Lewis, Jared C.,Li, Ying,Roux, Benoit,Upp, David M.
supporting information, p. 23672 - 23677 (2021/08/23)
Artificial metalloenzymes (ArMs) are commonly used to control the stereoselectivity of catalytic reactions, but controlling chemoselectivity remains challenging. In this study, we engineer a dirhodium ArM to catalyze diazo cross-coupling to form an alkene that, in a one-pot cascade reaction, is reduced to an alkane with high enantioselectivity (typically >99 % ee) by an alkene reductase. The numerous protein and small molecule components required for the cascade reaction had minimal effect on ArM catalysis. Directed evolution of the ArM led to improved yields and E/Z selectivities for a variety of substrates, which translated to cascade reaction yields. MD simulations of ArM variants were used to understand the structural role of the cofactor on ArM conformational dynamics. These results highlight the ability of ArMs to control both catalyst stereoselectivity and chemoselectivity to enable reactions in complex media that would otherwise lead to undesired side reactions.
Tropylium-Catalyzed O-H Insertion Reactions of Diazoalkanes with Carboxylic Acids
Empel, Claire,Nguyen, Thanh Vinh,Koenigs, Rene M.
supporting information, p. 548 - 553 (2021/01/26)
Herein, we describe the application of a nonbenzenoid aromatic carbocation, namely tropylium, as an organic Lewis acid catalyst in O-H functionalization reactions of diazoalkanes with benzoic acids. The newly developed protocol is applicable to a wide range of diazoalkane and carboxylic acid substrates with excellent efficiency (43 examples, up to 99% yield).
Visible-light-promoted selective: O -alkylation of 2-pyridones with α-aryldiazoacetates
Yang, Jingya,Wang, Ganggang,Zhou, Hongyan,Li, Zhifeng,Ma, Ben,Song, Menghui,Sun, Rongxia,Huo, Congde
supporting information, p. 394 - 398 (2021/01/29)
A visible-light-promoted O-H insertion reaction between 2-pyridones and α-aryldiazoacetates has been developed. Upon visible light irradiation, the reaction proceeds smoothly under mild and catalyst-free conditions. A wide scope of 2-pyridones and α-aryldiazoacetates are well tolerated, and various O-alkylated 2-pyridones are obtained with perfect selectivity and good functional group tolerance. A photoinduced radical process is probably responsible for the excellent selectivity. This journal is
