34706-60-0Relevant academic research and scientific papers
Silica-catalyzed carboxylative cyclization of propargylic amines with CO2
Matsuo, Hideaki,Choi, Jun-Chul,Fujitani, Tadahiro,Fujita, Ken-ichi
, (2020)
By employing only silica as a catalyst, the carboxylative cyclization of a propargylic amine with CO2 proceeded to afford the corresponding 2-oxazolidinone. MCM-41, which was a mesoporous silica, was found to be the most effective silica for th
Carboxylative cyclization of a propargylic amine with co2 catalyzed by a silica-coated magnetite
Matsuo, Hideaki,Choi, Jun-Chul,Fujitani, Tadahiro,Fujita, Ken-Ichi
, p. 698 - 701 (2021/07/09)
By employing a silica-coated magnetite as a catalyst, a silica-catalyzed carboxylative cyclization of propargylic amines with carbon dioxide (CO2) proceeded to afford the corresponding 2-oxazolidinones. Moreover, after the reaction, the silica-coated magn
Enantioselective Carboetherification/Hydrogenation for the Synthesis of Amino Alcohols via a Catalytically Formed Chiral Auxiliary
Buzzetti, Luca,Puri??, Mikus,Greenwood, Phillip D. G.,Waser, Jerome
, p. 17334 - 17339 (2020/11/02)
Chiral auxiliaries and asymmetric catalysis are the workhorses of enantioselective transformations, but they still remain limited in terms of either efficiency or generality. Herein, we present an alternative strategy for controlling the stereoselectivity of chemical reactions. Asymmetric catalysis is used to install a transient chiral auxiliary starting from achiral precursors, which then directs diastereoselective reactions. We apply this strategy to a palladium-catalyzed carboetherification/hydrogenation sequence on propargylic amines, providing fast access to enantioenriched chiral amino alcohols, important building blocks for medicinal chemistry and drug discovery. All stereoisomers of the product could be accessed by the choice of ligand and substituent on the propargylic amine, leading to a stereodivergent process.
Palladium-Catalyzed Carboxy-Alkynylation of Propargylic Amines Using Carbonate Salts as Carbon Dioxide Source
Greenwood, Phillip D. G.,Waser, Jerome
, p. 5183 - 5186 (2019/06/10)
A palladium-catalyzed multicomponent reaction of propargylic amines, alkynyl bromides and cesium hydrogen carbonate to access oxazolidinones is reported. In contrast to previous reports, only a slight excess of cesium hydrogen carbonate is used as a surrogate of carbon dioxide. The reaction gives access to oxazolidinones bearing alkyl- and aryl polysubstituted enynes in good yield and very high E stereoselectivity.
Efficient and Reusable Metal–Organic Framework Catalysts for Carboxylative Cyclization of Propargylamines with Carbon Dioxide
Zhao, Dan,Liu, Xiao-Hui,Zhu, Chendan,Kang, Yan-Shang,Wang, Peng,Shi, Zhuangzhi,Lu, Yi,Sun, Wei-Yin
, p. 4598 - 4606 (2017/12/04)
Carbon dioxide (CO2) capture and transformation are important for decreasing the concentration of atmospheric CO2. To effectively capture CO2 and further fix it into valuable chemical products, functionalized dynamic metal–organic frameworks (MOFs) have been utilized not only because of their inherent cavity for accommodating CO2 but also owing to their reversible structural transformations in response to external stimuli for regulating the reaction. Herein, we report a dynamic and functional MOF [Cd3(L)2(BDC)3]2?16 DMF (MOF-1 a; DMF=N,N-dimethylformamide) achieved by reaction of the amino tripodal imidazole ligand N1-(4-(1 H-imidazol-1-yl)benzyl)-N1- (2-aminoethyl)ethane-1,2-diamine (L) and 1,4-benzenedicarboxylic acid (H2BDC) with cadmium salt. MOF-1 a not only shows unprecedented high catalytic activity [initial turnover number (TON) up to 9300] and broad substrate scope for the carboxylative cyclization of propargylamines with CO2, but also can be switched on and off upon reversible structural transformation owing to its dynamic five-fold interpenetrating structure. Further studies demonstrate that MOF-1 a shows selective catalytic properties depending on the size of substrates, similarly to sophisticated biological systems.
Lanthanide-Catalyzed Reversible Alkynyl Exchange by Carbon–Carbon Single-Bond Cleavage Assisted by a Secondary Amino Group
Shao, Yinlin,Zhang, Fangjun,Zhang, Jie,Zhou, Xigeng
supporting information, p. 11485 - 11489 (2016/10/24)
Lanthanide-catalyzed alkynyl exchange through C?C single-bond cleavage assisted by a secondary amino group is reported. A lanthanide amido complex is proposed as a key intermediate, which undergoes unprecedented reversible β-alkynyl elimination followed by alkynyl exchange and imine reinsertion. The in situ homo- and cross-dimerization of the liberated alkyne can serve as an additional driving force to shift the metathesis equilibrium to completion. This reaction is formally complementary to conventional alkyne metathesis and allows the selective transformation of internal propargylamines into those bearing different substituents on the alkyne terminus in moderate to excellent yields under operationally simple reaction conditions.
Mechanistic Aspects of the Carboxylative Cyclization of Propargylamines and Carbon Dioxide Catalyzed by Gold(I) Complexes Bearing an N-Heterocyclic Carbene Ligand
Hase, Shun,Kayaki, Yoshihito,Ikariya, Takao
, p. 5135 - 5140 (2015/09/15)
The carboxylative cyclization of a range of propargylic amines using carbon dioxide (CO2) is promoted by IPr-gold(I) (IPr = 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene) complexes to afford (Z)-5-alkylidene-2-oxazolidones in methanol under mild conditions, even in the absence of additives such as silver salts and bases. Investigation of the substrate scope shows that the catalytic performance is markedly retarded by the introduction of aromatic substituents at the alkyne terminus. The formation of alkenylgold(I) complexes as catalytic intermediate models is demonstrated by the treatment of methyl- and phenyl-substituted propargylamines with AuOH(IPr) under a CO2 atmosphere. A comparison of the reactivity of the alkenylgold(I) complexes clearly indicates that the alkenyl ligand attached to an alkyl group at the α position is more susceptible to protonolysis compared with that attached to a phenyl group. These results and kinetic experiments corroborate a catalytic cycle that involves the nucleophilic attack of carbamate at the C-C triple bond bound to the Au center and its subsequent protodeauration to release the cyclic urethane products.
Ln[N(SiMe3)2]3-Catalyzed Cross-Diinsertion of C≡N/C≡C into an N-H Bond: Facile Synthesis of 1,2,4-Trisubstituted Imidazoles from Propargylamines and Nitriles
Hong, Longcheng,Shao, Yinlin,Zhang, Lixin,Zhou, Xigeng
, p. 8551 - 8555 (2014/07/21)
A lanthanide-catalyzed sequential insertion of C≡N and C≡C into an N-H bond is presented. The convenient reaction, which proceeds under mild conditions, is an efficient method for preparing 1,2,4-trisubstituted imidazoles directly from readily available propargylamines and nitriles.
Synthesis of bicyclic guanidines via cascade hydroamination/michael additions of mono- n -acryloylpropargylguanidines
Kwon, Ki-Hyeok,Serrano, Catherine M.,Koch, Michael,Barrows, Louis R.,Looper, Ryan E.
, p. 6048 - 6051 (2015/01/09)
A cascade silver(I)-catalyzed hydroamination/Michael addition sequence has been developed to deliver highly substituted bicyclic guanidines. This transformation gives rise to geometrically and constitutionally stable ene-guanidines and generates a remote stereocenter with moderate to high diastereoselectivity.
Synthesis of substituted 2-aminoimidazoles via Pd-catalyzed alkyne carboamination reactions. Application to the synthesis of preclathridine natural products
Zavesky, Blane P.,Babij, Nicholas R.,Wolfe, John P.
, p. 4952 - 4955 (2015/04/27)
A new method for the synthesis of 2-aminoimidazole products is described. The heterocyclic products are generated in good yields via Pd-catalyzed carboamination reactions of N-propargyl guanidines and aryl triflates. This methodology generates both a C-N
