- Gold-Catalyzed [3+2]-Annulations of α-Aryl Diazoketones with the Tetrasubstituted Alkenes of Cyclopentadienes: High Stereoselectivity and Enantioselectivity
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This work reports gold-catalyzed [3+2]-annulations of α-diazo ketones with highly substituted cyclopentadienes, affording bicyclic 2,3-dihydrofurans with high regio- and stereoselectivity. The reactions highlights the first success of tetrasubstituted alkenes to undergo [3+2]-annulations with α-diazo carbonyls. The enantioselective annulations are also achieved with high enantioselectivity using chiral forms of gold and phosphoric acid. Our mechanistic analysis supports that cyclopentadienes serve as nucleophiles to attack gold carbenes at the more substituted alkenes, yielding gold enolates that complex with chiral phosphoric acid to enhance the enantioselectivity.
- Chen, Ching-Nung,Cheng, Wei-Min,Wang, Jian-Kai,Chao, Tzu-Hsuan,Cheng, Mu-Jeng,Liu, Rai-Shung
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p. 4479 - 4484
(2021/01/21)
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- Photoinduced Diverse Reactivity of Diazo Compounds with Nitrosoarenes
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A diverse reactivity of diazo compounds with nitrosoarene in an oxygen-transfer process and a formal [2 + 2] cycloaddition is reported. Nitosoarene has been exploited as a mild oxygen source to oxidize an in situ generated carbene intermediate under visible-light irradiation. UV-light-mediated in situ generated ketenes react with nitosoarenes to deliver oxazetidine derivatives. These operationally simple processes exemplify a transition-metal-free and catalyst-free protocol to give structurally diverse α-ketoesters or oxazetidines.
- Roy, Sourav,Kumar, Gourav,Chatterjee, Indranil
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supporting information
p. 6709 - 6713
(2021/09/08)
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- Blue Light-Promoted N?H Insertion of Carbazoles, Pyrazoles and 1,2,3-Triazoles into Aryldiazoacetates
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Blue light irradiation of aryldiazoacetates leads to the formation of free carbenes, which can react with carbazoles, pyrazoles and 1,2,3-triazoles to afford the corresponding N?H inserted products. These reactions are performed under air and at room temperature, allowing the mild preparation of a variety of motifs found in biologically relevant targets. (Figure presented.).
- Stivanin, Mateus L.,Fernandes, Alessandra A. G.,da Silva, Amanda F.,Okada, Celso Y.,Jurberg, Igor D.
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p. 1106 - 1111
(2020/01/25)
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- Photochemical Doyle-Kirmse Reaction: A Route to Allenes
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This Letter describes the metal-free, blue-light-induced [2,3]-sigmatropic rearrangement of sulfonium ylides generated from donor/acceptor diazoalkanes and propargyl sulfides. The reaction furnishes highly functionalized allenes from a broad range of starting materials in decent yield. Mechanistic experiments supported by the literature data suggest singlet carbenes as intermediates in this reaction.
- Or?owska, Katarzyna,Rybicka-Jasińska, Katarzyna,Krajewski, Piotr,Gryko, Dorota
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supporting information
p. 1018 - 1021
(2020/01/31)
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- Controllable construction of isoquinolinedione and isocoumarin scaffolds: Via RhIII-catalyzed C-H annulation of N -tosylbenzamides with diazo compounds
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A highly efficient protocol for the synthesis of isoquinolinediones by RhIII-catalyzed C-H activation/annulation/decarboxylation of N-tosylbenzamides with diazo compounds is reported. The switchable synthesis of isocoumarins was also achieved successfully via C-H activation/annulation with slight modification of the reaction conditions. Importantly, the synthetic utility of this new reaction was further demonstrated in an atom-economical and operationally convenient total synthesis of a TDP2 inhibitor derivative from commercially available starting materials.
- Liu, Yanfei,Wu, Jiaping,Qian, Baiyang,Shang, Yongjia
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p. 8768 - 8777
(2019/10/16)
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- Au Nanoparticle-Catalyzed Insertion of Carbenes from α-Diazocarbonyl Compounds into Hydrosilanes
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Supported Au nanoparticles on TiO2 catalyze the insertion of carbenes from α-diazocabonyl compounds into hydrosilanes. It is proposed that the transformation involves two modes of catalytic activation: formation of nucleophilic Au carbenes on the surface of nanoparticle via expulsion of N2 and activation of the Si-H bond of hydrosilane on Au nanoparticle, followed by coupling of the chemisorbed species. No external ligands or additives are required, while the process is purely heterogeneous, thus allowing the recycling and reuse of the catalyst.
- Kidonakis, Marios,Stratakis, Manolis
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supporting information
p. 4086 - 4089
(2018/07/15)
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- Enantioselective Synthesis of 2,2,3-Trisubstituted Indolines via Bimetallic Relay Catalysis of α-Diazoketones with Enones
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An efficient asymmetric intramolecular trapping of ammonium ylides of α-diazoketones with enones to synthesize indoline derivatives was realized. A Rh(II)/chiral N,N′-dioxide-Sc(III) complex bimetallic relay catalytic system was established. A series of optically active 2,2,3-trisubstituted indolines were obtained in high yields (up to 99%), good enantioselectivities (up to 99% ee), and excellent diastereoselectivities (up to >19:1 dr) under mild reaction conditions.
- Yang, Jian,Ke, Chaoqi,Zhang, Dong,Liu, Xiaohua,Feng, Xiaoming
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supporting information
p. 4536 - 4539
(2018/08/07)
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- Copper-Catalyzed Carbenoid Insertion Reactions of α-Diazoesters and α-Diazoketones into Si-H and S-H Bonds
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An efficient copper-catalyzed carbenoid insertion reaction of α-diazo carbonyl compounds into Si-H and S-H bonds was developed. A wide range of α-silylesters and α-thioesters was obtained in high yields (up to 98%) from α-diazoesters using 5 mol% of a simple copper(I) salt as catalyst. Using 0.05 mol% of the same catalyst, α-diazoketones led to α-silylketones in low to good yields (up to 70%).
- Keipour, Hoda,Jalba, Angela,Delage-Laurin, Léo,Ollevier, Thierry
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p. 3000 - 3010
(2017/03/23)
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- Synthesis of Aryldiazoacetates through Palladium(0)-Catalyzed Deacylative Cross-Coupling of Aryl Iodides with Acyldiazoacetates
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Palladium(0)-catalyzed deacylative cross-coupling of aryl iodides and acyldiazocarbonyl compounds can be achieved at room temperature under mild reaction conditions. The coupling reaction represents a highly efficient and general method for the synthesis of aryldiazocarbonyl compounds, which have found wide and increasing applications as precursors for generating donor/acceptor-substituted metallocarbenes.
- Ye, Fei,Wang, Chengpeng,Zhang, Yan,Wang, Jianbo
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supporting information
p. 11625 - 11628
(2016/02/19)
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- Enantioselective N-H insertion reaction of α-aryl α-diazoketones: An efficient route to chiral α-aminoketones
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A highly enantioselective N-H insertion reaction of α-diazoketones was developed by using cooperative catalysis by dirhodium(II) carboxylates and chiral spiro phosphoric acids. The insertion reaction provides a new access route to diverse chiral α-aminoketones, which are versatile building blocks in organic synthesis, with fast reaction rates, good yields and high enantioselectivity under mild and neutral conditions. Spiro inspiration: A highly enantioselective N-H insertion reaction of α-diazoketones was developed by using cooperative catalysis by dirhodium(II) carboxylates and chiral spiro phosphoric acids. The insertion reaction provides a new access route to diverse chiral α-aminoketones, which are versatile building blocks in the organic synthesis, with fast reaction rates, good yields and high enantioselectivity under mild and neutral conditions.
- Xu, Bin,Zhu, Shou-Fei,Zuo, Xiao-Dong,Zhang, Zhi-Chao,Zhou, Qi-Lin
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supporting information
p. 3913 - 3916
(2014/05/06)
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- Synthesis of 2-aminofurans and 2-unsubstituted furans via carbenoid-mediated [3 + 2] cycloaddition
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An efficient dual synthetic manifold for 2-aminofurans and 2-unsubstituted furans has been developed. The carbenoid-mediated [3 + 2] cycloaddition of copper carbenoids with enamines provides 2-amino-2,3-dihydrofurans which serve as common intermediates for both 2-aminofurans and 2-unsubstituted furans. The Royal Society of Chemistry 2012.
- Jiang, Yaojia,Khong, Vanessa Zhong Yue,Lourdusamy, Emmanuvel,Park, Cheol-Min
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experimental part
p. 3133 - 3135
(2012/05/04)
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- Enantioselective reactions of donor/acceptor carbenoids derived from α-aryl-α-diazoketones
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The reaction of a variety of α-aryl-α-diazo ketones with activated olefins, catalyzed by the adamantyl glycine-derived dirhodium complex Rh2(S-PTAD)4, generates cyclopropyl ketones with high diastereoselectivity (up to >95:5 dr) and enantioselectivity (up to 98% ee). Intermolecular C-H functionalization of 1,4-cyclohexadiene by means of carbenoid-induced C-H insertion was also possible with this type of carbenoid.
- Denton, Justin R.,Davies, Huw M. L.
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supporting information; experimental part
p. 787 - 790
(2009/09/06)
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- A convenient preparation of diazo carbonyl compounds under tri-phase phase-transfer catalysis conditions
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A simple and convenient one-pot preparation method for pure diazo carbonyl compounds under tri-phase phase-transfer catalysis conditions is described.
- Madan Kumar
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p. 2121 - 2127
(2007/10/02)
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