327155-45-3Relevant academic research and scientific papers
Site-Selective 1,1-Difunctionalization of Unactivated Alkenes Enabled by Cationic Palladium Catalysis
Jeon, Jinwon,Ryu, Ho,Lee, Changseok,Cho, Dasol,Baik, Mu-Hyun,Hong, Sungwoo
, p. 10048 - 10059 (2019)
A palladium(II)-catalyzed 1,1-difunctionalization of unactivated terminal and internal alkenes via addition of two nucleophiles was developed using a cationic palladium(II) complex. The palladacycle generated in situ as a result of a regioselective addition of a nucleophile to the alkene can readily undergo regioselective β-hydride elimination and migratory insertion with a cationic palladium catalyst. The resulting η 3-π-allyl palladium(II) complex is the key intermediate that reacts with a second nucleophile to furnish the desired 1,1-difunctionalization of the alkene. Under the optimized reaction conditions, a wide range of indoles and anilines add to alkene units of 3-butenoic or 4-pentenoic acid derivatives to afford the synthetically useful γ,γ-or ?,?-difunctionalized products with excellent regiocontrol. Furthermore, by employing internal hydroxyl or acid groups and external carbon nucleophiles, this transformation enables unsymmetric 1,1-difunctionalization to forge challenging and important oxo quaternary carbon centers. Combining experiments and DFT calculations on the mechanism of the reaction is investigated in detail.
Site-Selective 1,1-Difunctionalization of Unactivated Alkenes Enabled by Cationic Palladium Catalysis
Jeon, Jinwon,Ryu, Ho,Lee, Changseok,Cho, Dasol,Baik, Mu-Hyun,Hong, Sungwoo
, (2019/07/03)
A palladium(II)-catalyzed 1,1-difunctionalization of unactivated terminal and internal alkenes via addition of two nucleophiles was developed using a cationic palladium(II) complex. The palladacycle generated in situ as a result of a regioselective addition of a nucleophile to the alkene can readily undergo regioselective β-hydride elimination and migratory insertion with a cationic palladium catalyst. The resulting η3-π-allyl palladium(II) complex is the key intermediate that reacts with a second nucleophile to furnish the desired 1,1-difunctionalization of the alkene. Under the optimized reaction conditions, a wide range of indoles and anilines add to alkene units of 3-butenoic or 4-pentenoic acid derivatives to afford the synthetically useful γ,γ- or δ,δ-difunctionalized products with excellent regiocontrol. Furthermore, by employing internal hydroxyl or acid groups and external carbon nucleophiles, this transformation enables unsymmetric 1,1-difunctionalization to forge challenging and important oxo quaternary carbon centers. Combining experiments and DFT calculations on the mechanism of the reaction is investigated in detail.
Phenolate-induced intramolecular ring-opening cyclization of: N -tosylaziridines: Access to functionalized benzoxacycles
Devi, Runjun,Das, Jonali,Sarma, Bipul,Das, Sajal Kumar
, p. 5846 - 5858 (2018/08/22)
Phenolate-induced, diastereo- and regioselective intramolecular exo-tet ring-opening cyclization of N-tosylaziridines has been achieved for the first time. The N-tosylaziridine substrates bearing a tethered (ortho-(tert-butyldimethylsiloxy))aryl substitue
Enantioselective copper-catalyzed intramolecular phenolic O-H bond insertion: Synthesis of chiral 2-carboxy dihydrobenzofurans, dihydrobenzopyrans, and tetrahydrobenzooxepines
Song, Xiao-Guang,Zhu, Shou-Fei,Xie, Xiu-Lan,Zhou, Qi-Lin
, p. 2555 - 2558 (2013/04/10)
Efficient: A copper-catalyzed enantioselective intramolecular insertion of carbenoids into phenolic O-H bonds has been developed. This method can be used for the synthesis of the title compounds in high yields and excellent enantioselectivities under mild and neutral conditions (see scheme). NaBAr F=sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. Copyright
Palladium-catalyzed addition of alcohol pronucleophiles to alkylidenecyclopropanes
Camacho,Nakamura,Saito,Yamamoto
, p. 270 - 275 (2007/10/03)
Palladium-catalyzed addition of alcohol pronucleophiles 1 to alkylidenecyclopropane derivatives afforded the corresponding allylic ethers 3 in excellent to moderate yields. Catalyst optimization indicated the Pd(PPh3)4-P(o-tolyl)3 combination as the best system among all catalysts tested. Intramolecular reaction also proceeded smoothly. A plausible mechanism for this catalytic reaction was proposed.
Intramolecular Enantioselective Palladium-Catalyzed Heck Arylation of Cyclic Enamides
Ripa, Lena,Hallberg, Anders
, p. 595 - 602 (2007/10/03)
Palladium-catalyzed intramolecular cyclization of N-formyl-6--1,2,3,4-tetrahydropyridine (1a) and N-formyl-6--1,2,3,4-tetrahydropyridine (1b) in the presence of AsPh3 resulted in formation of the spiro compounds N-formyl-3,3',4,4'-tetrahydrospiro (2a) and N-formyl-3',4'-dihydrospiro (2b), respectively, and in the presence of PPh3 and TlOAc in the spiro compounds N-formyl-3,4,5',6'-tetrahydrospiro (3a) and N-formyl-5',6'-dihydrospiro (3b), respectively.Cyclization of N-formyl-6-(3-phenyl>propyl)-1,2,3,4-tetrahydropyridine (7) in presence of a chiral (phosphinoaryl)oxazoline ((S)-8) resulted in formation of (R)-3a and (R)-N-formyl-1',3,4,6'-tetrahydrospiro ((R)-6a) in high enantiomeric excesses, 87 percent and >99percent, respectively, and in good yield.The oxazoline ligand (S)-8 furnished higher enantiomeric excesses and improved regioselectivities than (R)-BINAP.
