176384-79-5Relevant academic research and scientific papers
Photocatalyzed Diastereoselective Isomerization of Cinnamyl Chlorides to Cyclopropanes
Dykstra, Ryan,Gutierrez, Osvaldo,Martin, Robert T.,Tambar, Uttam K.,Troian-Gautier, Ludovic,Xu, Bin
supporting information, p. 6206 - 6215 (2020/04/27)
Endergonic isomerizations are thermodynamically unfavored processes that are difficult to realize under thermal conditions. We report a photocatalytic and diastereoselective isomerization of acyclic cinnamyl chlorides to strained cyclopropanes. Quantum mechanical calculations (uM06-2X and DLPNO), including TD-DFT calculations, and experimental studies provide evidence for the energy transfer from an iridium photocatalyst to the allylic chloride substrate followed by C-Cl homolytic cleavage. Subsequent Cla￠ radical migration forms a localized triplet 1,3-diradical intermediate that, after intersystem crossing, undergoes ring-closing to form the desired product. The mild reaction conditions are compatible with a broad range of functional groups to generate chlorocyclopropanes in high yields and diastereoselectivities. A more efficient process is developed by addition of a catalytic amount of a nickel complex, and we propose a novel role for this cocatalyst to recycle an allyl chloride byproduct generated in the course of the reaction. The reaction is also shown to be stereoconvergent, as an E/Z mixture of cinnamyl chlorides furnish the anti-chlorocyclopropane product in high diastereoselectivity. We anticipate that the use of a visible light activated photocatalyst to transform substrates in combination with a transition metal catalyst to recycle byproducts back into the catalytic cycle will provide unique opportunities for the discovery of new reactivity.
Gold-Catalyzed Aminoaromatizations of 1,2-Bis(alkynyl)benzenes with Anthranils to Yield 1-Amino-2-napthaldehyde Products
Pandit, Yashwant Bhaskar,Liu, Rai-Shung
, p. 3183 - 3189 (2020/07/13)
Gold-catalyzed aminoaromatizations of 1,n-diynes with anthranils afforded 1-amino-2-napthaldehyde derivatives efficiently. In this reaction sequence, anthranils preferably attack at gold-coordinated prop-3-yn-1-ols to generate α-imino gold carbenes that e
Palladium-catalyzed multicomponent reaction (MCR) of propargylic carbonates with isocyanides
Peng, Jianwen,Gao, Yang,Hu, Weigao,Gao, Yinglan,Hu, Miao,Wu, Wanqing,Ren, Yanwei,Jiang, Huanfeng
supporting information, p. 5924 - 5927 (2016/11/29)
A palladium-catalyzed multicomponent reaction (MCR) of propargylic carbonates with isocyanides is reported. Remarkably, the orderly insertion of isocyanides affords two types of valuable N-heterocyclic products (Z)-6-imino-4,6-dihydro-1H-furo[3,4-b]pyrrol-2-amines and (E)-5-iminopyrrolones in high yields. Systematic analysis of the reaction conditions indicates that the selectivity of these N-heterocyclic products can be controlled by ligands and temperature.
Synthesis of angularly fused aromatic compounds from alkenyl enediynes by a tandem radical cyclization process
Roy, Snigdha,Anoop, Anakuthil,Biradha, Kumar,Basak, Amit
supporting information; experimental part, p. 8316 - 8319 (2011/10/09)
Let's get radical: A general synthetic route toward angularly ortho-fused polyaromatic [4]helicenes starting from aryl alkenyl N-substituted cyclic enediynes is described (see scheme; DMSO=dimethyl sulfoxide, Ns=4-nitrobenzenesulfonyl). The process involved a Bergman cyclization (BC) as the key step of an unprecedented tandem radical reaction.
Memory of chirality in cascade rearrangements of enediynes
Nechab, Malek,Campolo, Damien,Maury, Julien,Perfetti, Patricia,Vanthuyne, Nicolas,Siri, Didier,Bertrand, Michele P.
supporting information; experimental part, p. 14742 - 14744 (2011/02/16)
The cascade rearrangement of chiral enediynes 1c-e, involving successively 1,3-proton shift, Saito-Myers cyclization, 1,5-hydrogen atom transfer, and intramolecular coupling of the resulting biradical, proceeded at 80°C to form tri- and tetracyclic heterocycles possessing a quaternary stereogenic center with a very high level of memory of chirality.
Synthesis and aromatisation of cyclic enediyne-containing amino acids
Kaiser, Jasper,Van Esseveldt, Bart C. J.,Segers, Margot J. A.,Van Delft, Floris L.,Smits, Jan M. M.,Butterworth, Sam,Rutjes, Floris P. J. T.
experimental part, p. 695 - 705 (2009/06/19)
A series of cyclic enediyne-containing amino acids with ring sizes varying from 10 to 12 atoms have been prepared starting from propargylglycine and homopropargylglycine. Their reactivity towards Bergman cyclisation under elevated temperatures has been ex
Catalytic enantioselective synthesis of chiral tetraphenylenes: Consecutive inter- and intramolecular cycloadditions of two triynes
Shibata, Takanori,Chiba, Tatsuya,Hirashima, Hiroyuki,Ueno, Yasunori,Endo, Kohei
supporting information; experimental part, p. 8066 - 8069 (2010/02/27)
Triynes having a phenylene-bridged 1,5-diyne moiety were transformed into substituted tetraphenylenes by the title sequence. A cationic Rh-ligand species catalyzed this highly enantioselective reaction. This protocol is a new and easy approach to the cons
Design, synthesis and biological evaluations of a novel series of enediynes constituted with DNA cleavage, alkylating and DNA binding agents via varies spacers
Linb, Chi-Fong,Hwanga, Martin,Kuo, Yao-Haur,Wu, Ming-Jung
, p. 525 - 532 (2008/02/11)
Among the three series of complicated combinatory enediynes, 3a-d were more active than 2a-c and 4a-b, in which 3a-b showed equally inhibitory activity against the growth of Hepa59T/VGH, KB and Hela with mean IC50 values lower than 10 μg/mL. Co
Synthesis and DNA damaging ability of enediyne model compounds possessing photo-triggering devices
Suzuki, Ichiro,Uno, Shinsaku,Tsuchiya, Yuko,Shigenaga, Akira,Nemoto, Hisao,Shibuya, Masayuki
, p. 2959 - 2962 (2007/10/03)
Enediyne model compounds possessing photo-triggering devices were developed. These enediynes afforded biradicals by UV irradiation and showed DNA cleaving activity. The DNA damage was confirmed to be mainly caused by the biradical, not singlet oxygen.
Allene-eneyne Related Cycloaromatization: Design and Synthesis of New DNA-cleaving Compounds
Wu, Ming-Jung,Lin, Chi-Fong,Jing, Pao-Tzu,Chang, Li-Juan,Duh, Tsai-Hui,Lee, Fang-Chen,Chen, Huey-Ting
, p. 475 - 479 (2007/10/03)
(Z)-7-Sulfonyl-3-hexen-1,5-diyne containing molecules are stable at room temperature and isomerized to eneyne-allene-sulfones under alkaline conditions. These eneyne-allene-sulfones were not isolable, spontaneously cyclized to form biradical intermediates under mild conditions, and exhibited good DNA-cleaving and human tumor cell line growth inhibition properties. Further studies indicated that compounds bearing on aromatic ring at C(3) and C(4), such as 25, proved to be more active against those tumor cell lines. ReEndocrinology moval of acetylene unit at C(1) and C(2), made the resulting compound less active. A related compound, (Z,Z)-12-(2-tetrahydropyranyl)oxy-1-phenylsulfonyldodeca-4,8-diene-2,6,10-triyne (37), was synthesized. Upon treatment of triethylamine at refluxing benzene, this compound undergoes double cycloaromatization to form a naphalene adduct, which possesses excellent DNA-cleaving activity.
