124517-47-1Relevant articles and documents
Sustainable Palladium-Catalyzed Tsuji-Trost Reactions Enabled by Aqueous Micellar Catalysis
Braga, Felipe C.,Gallou, Fabrice,Lee, Nicholas R.,Lippincott, Daniel J.,Lipshutz, Bruce H.,Moghadam, Farbod A.,Zhu, Bingchun
supporting information, (2020/07/15)
Palladium-catalyzed allylic substitution, or "Tsuji-Trost"reactions, can be run under micellar catalysis conditions featuring not only chemistry in water but also numerous combinations of reaction partners that require low levels of palladium, typically on the order of 1000 ppm (0.1 mol %). These couplings are further characterized by especially mild conditions, leading to a number of cases not previously reported in an aqueous micellar medium. Inclusion of diverse nucleophiles, such as N-H heterocycles, alcohols, dicarbonyl compounds, and sulfonamides is described. Intramolecular cyclizations further illustrate the broad utility of this process. In addition to recycling studies, a multigram scale example is reported, indicative of the prospects for scale up.
Synthesis of Amide Enol Carbamates and Carbonates through Cu(OTf)2-Catalyzed Reactions of Ynamides with t-Butyl Carbamates/Carbonates
Han, Pan,Mao, Zhuo-Ya,Li, Ming,Si, Chang-Mei,Wei, Bang-Guo,Lin, Guo-Qiang
, p. 4740 - 4752 (2020/04/30)
A highly regioselective approach to access amide enol carbamates and carbonates 5a-5c′, 7a-7h, and 9 was developed through Cu(OTf)2-catalyzed reactions of ynamides 4 with t-butyl carbamates 2 and 8 and t-butyl carbonates 6. Moreover, this strategy was successfully applied to generate amide enol carbamates 11a-11s and 14a-14f from imides 10 and 13 with ynamides through an N-Boc cleavage-addition ring-opening process. A range of substituents was amenable to this transformation, and the desired amide enol carbamates and carbonates were obtained in moderate to good yields.
Asymmetric Synthesis of α-Quaternary γ-Lactams through Palladium-Catalyzed Asymmetric Allylic Alkylation
Song, Tao,Arseniyadis, Stellios,Cossy, Janine
supporting information, p. 603 - 607 (2019/02/28)
The synthesis of chiral unsaturated γ-lactams is reported featuring a highly enantioselective palladium-catalyzed asymmetric allylic alkylation of α, γ-disubstituted 2-silyloxypyrroles. This method allows a straightforward access to optically active γ-lactams bearing an α-quaternary stereogenic center in high yields (up to 93%), high regioselectivities (up to >20:1), and excellent enantioselectivities (up to 95% ee). To further demonstrate the synthetic utility of the method, the resulting allylated products were converted to various versatile chiral building blocks, such as pyrrolidines and pyrrolidinones.
Enantioselective iridium catalyzed α-alkylation of azlactones by a tandem asymmetric allylic alkylation/aza-Cope rearrangement
Bai, Xue-Dan,Zhang, Qing-Feng,He, Ying
supporting information, p. 5547 - 5550 (2019/05/21)
The development of an iridium catalyzed enantioselective α-alkylation of azlactones has been described. The reaction provides rapid access to a wide range of enantio-enriched quaternary carbon center allylated 2,4-diaryloxazol-5(2H)-ones in excellent yiel
Asymmetric Dearomatization/Cyclization Enables Access to Polycyclic Chemotypes
Hayashi, Mikayo,Brown, Lauren E.,Porco, John A.
supporting information, p. 4800 - 4804 (2016/10/13)
Enantioenriched, polycyclic compounds were obtained from a simple acylphloroglucinol scaffold. Highly enantioselective dearomatization was accomplished using a Trost ligand–palladium(0) complex. A computational DFT model was developed to rationalize observed enantioselectivities and revealed a key reactant-ligand hydrogen bonding interaction. Dearomatized products were used in visible light-mediated photocycloadditions and oxidative free radical cyclizations to obtain novel polycyclic chemotypes including tricyclo[4.3.1.01,4]decan-10-ones, bicyclo[3.2.1]octan-8-ones and highly substituted cycloheptanones.
Iridium-catalyzed allyl-allyl cross-coupling of allylic carbonates with (E)-1,3-diarylpropenes
Yuan, Qianjia,Yao, Kun,Liu, Delong,Zhang, Wanbin
supporting information, p. 11834 - 11836 (2015/07/15)
An efficient Ir-catalyzed allyl-allyl cross-coupling reaction of allylic carbonates with (E)-1,3-diarylpropenes was developed to form linear allylated products, 1,5-dienes, regioselectively in excellent yields and with high turnover numbers (up to 2000 S/
Branched/linear selectivity in palladium-catalyzed allyl-allyl cross-couplings: the role of ligands
Ardolino, Michael J.,Morken, James P.
supporting information, p. 6409 - 6413 (2015/08/18)
Abstract While Pd-catalyzed allyl-allyl cross-couplings in the presence of small-bite-angle bidentate ligands reliably furnish the branched regioisomer with high levels of selectivity, cross-couplings in the presence of large-bite-angle bidentate ligands
Congested C-C bonds by Pd-catalyzed enantioselective allyl-allyl cross-coupling, a mechanism-guided solution
Ardolino, Michael J.,Morken, James P.
supporting information, p. 7092 - 7100 (2014/06/09)
Under the influence of a chiral bidentate diphosphine ligand, the Pd-catalyzed asymmetric cross-coupling of allylboron reagents and allylic electrophiles establishes 1,5-dienes with adjacent stereocenters in high regio-and stereoselectivity. A mechanistic study of the coupling utilizing reaction calorimetry and density functional theory analysis suggests that the reaction operates through an inner-sphere 3,3′-reductive elimination pathway, which is both rate-defining and stereodefining. Coupled with optimized reaction conditions, this mechanistic detail is used to expand the scope of allyl-allyl couplings to allow the generation of 1,5-dienes with tertiary centers adjacent to quaternary centers as well as a unique set of cyclic structures.
Mixed metal MgO-ZrO2 nanoparticle-catalyzed O-tert-Boc protection of alcohols and phenols under solvent-free conditions
Gawande, Manoj B.,Shelke, Sharad N.,Branco, Paula S.,Rathi, Anuj,Pandey, Rajesh K.
experimental part, p. 395 - 400 (2012/09/25)
An environmentally benign method for O-tert-Boc protection of alcohols and phenols catalyzed by MgO-ZrO2 nanoparticles under solvent-free conditions is described. A variety of phenols, alcohols (aliphatic and aromatic) were converted to corresponding O-tert-Boc products in good to excellent yield (50-95%). The present protocol is expedient, simple, and efficient under solvent-free conditions. The MgO-ZrO2 Nps are easily prepared from inexpensive precursors, and are reusable, recyclable and chemoselective. Copyright 2012 John Wiley & Sons, Ltd. Copyright
Iridium-catalyzed, regio- and enantioselective allylic substitution with aromatic and aliphatic sulfinates
Ueda, Mitsuhiro,Hartwig, John F.
supporting information; experimental part, p. 92 - 94 (2010/03/04)
"Chemical Equation Presented" The iridium-catalyzed allylation of sodium sulfinate to form branched allylic sulfones is reported. The reactions between various sodium sulfinates and achiral allylic carbonates occur in good yields, with high selectivity fo
