324738-55-8Relevant academic research and scientific papers
Palladium-Catalyzed Carbamoyl-Carbamoylation/ Carboxylation/Thioesterification of Alkene-Tethered Carbamoyl Chlorides Using Mo(CO)6 as the Carbonyl Source
Chen, Chen,Huang, Yujie,Ding, Jie,Liu, Liying,Zhu, Bolin
, p. 794 - 801 (2022/01/04)
We reported a palladium-catalyzed carbamoyl-carbamoylation/carboxylation/thioesterification of alkene-tethered carbamoyl chlorides using Mo(CO)6 as the carbonyl source. The reactions were typically performed with good functional group compatibility and tolerated different nucleophiles (amines, alcohols, phenols, thiols and water), which provided a new access to amidated/esterificated/thioesterificated/carboxylated oxindoles or lactams bearing an all-carbon quaternary stereocenter under CO gas-free conditions. Furthermore, natural product mutation and divergent late-stage derivatization are the important practical features.
Palladium-Catalyzed Phosphoryl-Carbamoylation of Alkenes: Construction of Nonbenzylic C(sp3)?P(O)R2 Bonds via C(sp3)?Pd(II)?P(O)R2 Reductive Elimination
Chen, Chen,Sun, Wan,Yan, Yan,Yang, Fang,Wang, Yuebo,Zhu, Yan-Ping,Liu, Liying,Zhu, Bolin
, p. 2970 - 2975 (2020/07/06)
We report the first example of palladium-catalyzed phosphoryl-carbamoylation of alkene-tethered carbamoyl chlorides with P(O)H compounds. Both H-phosphinates and secondary phosphine oxides are compatible with this reaction. DPE-Phos was used as ligand to facilitate nonbenzylic C(sp3)?P bonds formations via C(sp3)?Pd(II)?P reductive elimination. By using this protocol, a range of phosphorylated oxindoles and lactams were obtained in moderate to good yields. (Figure presented.).
Chemoselectivity for Alkene Cleavage by Palladium-Catalyzed Intramolecular Diazo Group Transfer from Azide to Alkene
Frost, Grant B.,Mittelstaedt, Michaela N.,Douglas, Christopher J.
, p. 1727 - 1732 (2019/01/09)
Alkenes can be cleaved by means of the (3+2) cycloaddition and subsequent cycloreversion of 1,3-dipoles, classically ozone (O3), but the azide (R?N3) variant is rare. Chemoselectivity for these azide to alkene diazo group transfers (DGT) is typically disfavored, thus limiting their synthetic utility. Herein, this work discloses a palladium-catalyzed intramolecular azide to alkene DGT, which grants chemoselectivity over competing aziridination. The data support a catalytic cycloreversion mechanism distinct from other known metal-catalyzed azide/alkene reactions: nitrenoid/metalloradical and (3+2) cycloadditions. Kinetics experiments reveal an unusual mechanistic profile in which the catalyst is not operative during the rate-controlling step, rather, it is active during the product-determining step. Catalytic DGT was used to synthesize N-heterocyclic quinazolinones, a medicinally relevant structural core. We also report on the competing aziridination and subsequent ring expansion to another N-heterocyclic core structure of interest, benzodiazepinones.
Synthesis of substituted γ-lactam via Pd(0)-catalyzed cyclization of alkene-tethered carbamoyl chloride
Chen, Chen,Hu, Jian,Su, Jianhua,Tong, Xiaofeng
, p. 3229 - 3231 (2014/06/09)
Pd(0)-catalyzed carboiodonation of but-3-enylcarbamic chloride has been developed with NaI as additive, which provides a ready access to substituted γ-lactam bearing an alkyl iodide group. This reaction features alkyl iodide reductive elimination as a key step in catalytic cycle, indicating the crucial role of additive NaI.
Enantioselective synthesis of 3,3-disubstituted oxindoles through pd-catalyzed cyanoamidation
Yasui, Yoshizumi,Kamisaki, Haruhi,Takemoto, Yoshiji
supporting information; experimental part, p. 3303 - 3306 (2009/05/07)
(Chemical Equation Presented) The first enantioselective cyanoamidation of olefins provides quick access to a variety of 3,3-disubstituted oxindoles. The combination of Pd(dba)2, an optically active phosphoramidite, and N,N-dimethylpropylene urea (DMPU) i
Intramolecular cyanoamidation of unsaturated cyanoformamides catalyzed by palladium: an efficient synthesis of multi-functionalized lactams
Kobayashi, Yusuke,Kamisaki, Haruhi,Takeda, Hiroshi,Yasui, Yoshizumi,Yanada, Reiko,Takemoto, Yoshiji
, p. 2978 - 2989 (2007/10/03)
The Pd(0)-catalyzed intramolecular cyanoamidation of several unsaturated cyanoformamides with alkenyl, allenyl, and alkynyl groups was investigated. In the cases of alkynyl and 1,1-disubstituted alkenyl cyanoformamides, the Pd(0)-catalyzed C-CN activation and subsequent insertion reaction proceeded smoothly and gave the corresponding lactams bearing a cyano group at the β-position in good yields. The mechanism of the reaction was also discussed.
Palladium catalysed tandem cyclisation-anion capture processes. Part 8 [1]: In situ and preformed organostannanes. Carbamyl chlorides and other starter species
Anwar, Usman,Fielding, Mark R.,Grigg, Ronald,Sridharan, Visuvanathar,Urch, Christopher J.
, p. 1476 - 1487 (2007/10/03)
A sequential one-pot process is reported involving in situ, palladium catalysed, formation of a series of tributylstannyl-1,2-carbo and heterocyclic dialkylidene-5-membered rings from the corresponding 1,6-diynes and Bu 3SnH. These substrates a
Generation and cyclization of unsaturated carbamoyl radicals derived from S-4-pentynyl carbamothioates under tin-free conditions
Benati, Luisa,Bencivenni, Giorgio,Leardini, Rino,Minozzi, Matteo,Nanni, Daniele,Scialpi, Rosanna,Spagnolo, Piero,Zanardi, Giuseppe
, p. 3192 - 3197 (2007/10/03)
The radical reaction of benzenethiol with S-4-pentynyl carbamothioates provides a valuable protocol for the tin-free generation of carbamoyl radicals, which arise from intramolecular substitution at sulfur by the initial sulfanylvinyl radicals. This procedure can be usefully employed to achieve N-benzylcarbamoyl radical 5-exo and 4-exo cyclizations leading, respectively, to pyrrolidinones and azetidinones, although, for the latter, it seems of lesser utility. Novel evidence is presented that. N-tosyl-substituted carbamoyl radicals display a peculiar tendency to yield the corresponding isocyanate by β-elimination of the tosyl radical.
Novel synthesis of oxindoles from carbamoyl chlorides via palladium catalysed cyclisation-anion capture
Fielding,Grigg,Urch
, p. 2239 - 2240 (2007/10/03)
The synthesis of 3,3-disubstituted and 3-methyleneox-indoles by palladium(0) catalysed cyclisation of carbamoyl chlorides onto proximate alkene or alkyne groups has been achieved in good yields.
