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.
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).
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
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.
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.
Rhodium-Catalyzed [4+2] Annulation of N-Aryl Pyrazolones with Diazo Compounds To Access Pyrazolone-Fused Cinnolines
Dhole, Sandip,Huang, Wan-Wen,Huang, Ying-Ti,Lin, Chih-Yu,Sun, Chung-Ming
supporting information, p. 4984 - 4992 (2021/09/28)
An efficient synthesis of novel dinitrogen-fused heterocycles such as pyrazolo[1,2-a]cinnoline derivatives have been accomplished by the rhodium(III)-catalyzed reaction of N-arylpyrazol-5-ones with α-diazo compounds. This reaction proceeds through a cascade C?H activation/intramolecular cyclization with a broad substrate scope. Furthermore, this protocol is successfully extended to the unusual phosphorus-containing α-diazo compounds and cyclic diazo compounds as the cross-coupling partners to deliver the two new kinds of pyrazolo[1,2-a]cinnolinones. The control experiments were performed to reveal insight into the mechanism of this reaction, involving reversible C?H activation, migratory insertion of the diazo compound, and cascade cyclization as the key steps of the transformation. Moreover, gram-scale synthesis and further transformation of the target product demonstrate the synthetic utility of the present protocol.
