6773-29-1Relevant articles and documents
Reactions of donor-acceptor cyclopropanes or benzylidenemalonate with benzyl azide by generating gallium trichloride 1,2-zwitterionic complexes
Borisova,Tarasova,Potapov,Novikov,Tomilov, Yu. V.
, p. 1504 - 1509 (2019)
The reactions of 1,2-zwitterionic complexes, generated from 2-arylcyclopropane-1,1-dicarboxylates (ACDC) or benzylidenemalonate and gallium trichloride, with benzyl azide proceeds as a formal [3+2] cycloaddition to form dihydro-1,2,3-triazoles. The latter, when the reaction mixture is treated with 10% aqueous HCl, undergo retrocyclization with elimination of diazomalonate. The reaction of ACDC, benzyl azide, and GaCl3 with simultaneous mixing of the reagents leads to the interception of the 1,3-zwitterion, with this stage being accompanied by both the cyclization to substituted 1,2,3-triazinine and the elimination of a nitrogen molecule to form 3,4-dihydro-2H-1,2-oxazine structure, which after acid hydrolysis gives substituted 3-hydroxypyrrolidin-2-one.
4,5-Dialkyl-substituted 3-oxo-(2H)-isothiazole 1,1-dioxides in reactions with diazomethane
Rodina,Gidon,Nikolaev,Shulze
, p. 466 - 473 (2008)
It has been established that the interaction of diazomethane with 4,5-dialkyl-substituted 3-oxo-(2H)-isothiazole 1,1-dioxides proceeds in two stages. Initially alkylation of the sulfonimide nitrogen atom and the carbonyl group oxygen atom occurs (in a ratio of ～ 3:2), then there is a regioselective cycloaddition of diazomethane at the C=C double bond with the formation of the corresponding N-methyloxoisothiazolopyrazolines and 3-methoxyisothiazolopyrazolines.
A Cyclopropene Electrophile that Targets Glutathione S-Transferase Omega-1 in Cells
W?rmer, Gustav J.,Hansen, Bente K.,Palmfeldt, Johan,Poulsen, Thomas B.
, p. 11918 - 11922 (2019)
Cyclopropenes are an important new addition to the portfolio of functional groups that can be used for bioorthogonal couplings. The inert nature of these highly strained compounds in complex biological systems is almost counterintuitive given their established electrophilic properties in organic synthesis. Here we provide the first demonstration of a cyclopropene that is capable of direct conjugation to protein targets in cells and show that this compound preferentially alkylates the active site cysteine of glutathione S-transferase omega-1 (GSTO1).
A Practical Synthesis of Valuable Strained Eight-Membered-Ring Derivatives for Click Chemistry
Bernard, Sabrina,Kumar, Ramar Arun,Porte, Karine,Thuéry, Pierre,Taran, Frédéric,Audisio, Davide
, p. 2000 - 2008 (2018)
A convenient and cost-effective synthetic access to cyclooctyne and trans-cyclooctene derivatives is described. A cyclopropanation step using copper powder in place of Rh2(OAc)4 as catalyst and a symmetric diazomalonate resulted in a drastic decrease in the overall cost of the synthesis. Further derivatizations allowed us to characterize, for the first time, the structure of a BCN analogue by X-ray crystallography, and to obtain a library of derivatives that could potentially be useful for applications in metal-free click chemistry.
Two Catalytic Methods of an Asymmetric Wittig [2,3]-Rearrangement
O?eka, Maksim,Kimm, Mariliis,J?rving, Ivar,Lippur, Kristin,Kanger, T?nis
, p. 2889 - 2897 (2017)
Two different approaches for asymmetric catalytic Wittig [2,3]-rearrangement were developed. Allyloxymalonate derivatives were converted into homoallyl alcohols via organocatalytic or Ca2+-catalyzed pathways in moderate to high enantioselectivi
Selective Chain-End Functionalization of Polar Polyethylenes: Orthogonal Reactivity of Carbene and Polar Vinyl Monomers in Their Copolymerization with Ethylene
Wang, Xiaoming,Nozaki, Kyoko
, p. 15635 - 15640 (2018)
Pd(II)-catalyzed copolymerization of ethylene, carbene species, and polar vinyl monomers is successfully developed for the first time to obtain chain-end-functionalized polar polyethylenes, with selective distribution of the polar vinyl monomers within the main chain and carbene at the chain-end. Notably, >99% chain-end-capping with the carbene species can be achieved under the optimized conditions. Mechanistic investigations suggest that the carbene precursor reacts with the generated alkyl palladium complex to terminate the growing chain-end and regenerate the catalyst.
Azide Radical Initiated Ring Opening of Cyclopropenes Leading to Alkenyl Nitriles and Polycyclic Aromatic Compounds
Muriel, Bastian,Waser, Jerome
supporting information, p. 4075 - 4079 (2021/01/18)
We report herein a radical-mediated amination of cyclopropenes. The transformation proceeds through a cleavage of the three-membered ring after the addition of an azide radical on the strained double bond and leads to tetrasubstituted alkenyl nitrile derivatives upon loss of N2. With 1,2-diaryl substituted cyclopropenes, this methodology could be extended to a one-pot synthesis of highly functionalized polycyclic aromatic compounds (PACs). This transformation allows the synthesis of nitrile-substituted alkenes and aromatic compounds from rapidly accessed cyclopropenes using only commercially available reagents.
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.
Iridium(III)-Catalyzed C(3)-H Alkylation of Isoquinolines via Metal Carbene Migratory Insertion
Jha, Neha,Singh, Roushan Prakash,Saxena, Paridhi,Kapur, Manmohan
supporting information, p. 8694 - 8698 (2021/11/24)
An Ir(III)-catalyzed C(3)-H alkylation of N-acetyl-1,2-dihydroisoquinolines with diverse acceptor-acceptor diazo compounds has been achieved under a single catalytic system via metal carbene migratory insertion. Moreover, further synthetic transformations of the alkylated products such as aromatization, selective decarboxylation, and decarbonylation lead to the formation of several synthetically viable isoquinoline derivatives having immense potentials.
Amino-modified Merrifield resins as recyclable catalysts for the safe and sustainable preparation of functionalized α-diazo carbonyl compounds
Fantinel, Mariane,Valiati, Nayara,Moro, Pedro A.M.,Sá, Marcus M.
, (2021/03/30)
Amino-functionalized polystyrene polymers derived from Merrifield resins were prepared and characterized. These basic materials were successfully employed as heterogeneous catalysts in the diazo transfer reaction to 1,3-dicarbonyl compounds, furnishing the corresponding diazo compounds in good to excellent yields and in relatively short reaction times. In addition, the work-up and purification protocols are simple and do not generate large amounts of waste, which are important features in sustainable catalysis and environmentally benign processes. The feasibility of the recovery and reuse of the amino-modified catalysts was also verified, since they can be employed up to five times without appreciable loss of catalytic activity. This straightforward procedure can be readily scaled up to gram scale, enabling the wide application of this method. The synthetic potential was demonstrated through the two-step preparation of 2-amino-N-dodecylacetamide (ANDA), a small molecule of commercial relevance.
