2972-25-0Relevant articles and documents
Palladium(II)-Catalyzed Enantioselective Arylation of Unbiased Methylene C(sp3)?H Bonds Enabled by a 2-Pyridinylisopropyl Auxiliary and Chiral Phosphoric Acids
Yan, Sheng-Yi,Han, Ye-Qiang,Yao, Qi-Jun,Nie, Xing-Liang,Liu, Lei,Shi, Bing-Feng
, p. 9093 - 9097 (2018/07/25)
Enantioselective functionalizations of unbiased methylene C(sp3)?H bonds of linear systems by metal insertion are intrinsically challenging and remain a largely unsolved problem. Herein, we report a palladium(II)-catalyzed enantioselective arylation of unbiased methylene β-C(sp3)?H bonds enabled by the combination of a strongly coordinating bidentate PIP auxiliary with a monodentate chiral phosphoric acid (CPA). The synergistic effect between the PIP auxiliary and the non-C2-symmetric CPA is crucial for effective stereocontrol. A broad range of aliphatic carboxylic acids and aryl bromides can be used, providing β-arylated aliphatic carboxylic acid derivatives in high yields (up to 96 %) with good enantioselectivities (up to 95:5 e.r.). Notably, this reaction also represents the first palladium(II)-catalyzed enantioselective C?H activation with less reactive and cost-effective aryl bromides as the arylating reagents. Mechanistic studies suggest that a single CPA is involved in the stereodetermining C?H palladation step.
Some Aspects of the Chemistry of Benzosuberone: Novel synthesis of the 5,9-methano-5H-benzocycloheptene and 6,9-ethano-5H-benzocycloheptene ring systems.
Omar, Mahmoud T.,Proctor, George R.,Scopes, David I. C.
, p. 2918 - 2949 (2007/10/02)
5-Cyano-7-(dimethylamino)-5-phenylheptanoic acid (3; R1=H, R2=CN) and its derivatives could not be cyclised to benzosuberones but yielded with PPA, 3-(dimethylaminoethyl)-3-phenyl-2,7(1H)-dioxoazepane (6) and 6-(dimethylaminoethyl)-6
LIGHT-INDUCED FREE-RADICAL REACTIONS OF 2-METHOXY-6-METHYLTETRAHYDROPYRAN: IRREVERSIBLE RING OPENING AND MULTISITE HYDROGEN ABSTRACTION
Babcock, Bruce W.,Dimmel, Donald R.,Graves, David P.,McKelvey, Ronald D.
, p. 736 - 742 (2007/10/02)
Acetophenone-initiated photodegradation of cis-2-methoxy-4-methyltetrahydropyran (7) in benzene solvent produced six products.The structures of the products, and studies using optically active 7, showed that hydrogen abstraction occurs at both C-2 and C-6 of the tetrahydropyran ring.The products derived from the C-2 radical indicated two pathways for this radical: ring opening and loss of methyl, which is consistent with previous work on other similar systems.Results with optically active 7 showed that the ring-opening pathway is irreversible.Generation of an open-chain radical independently also showed that cyclization to a six membered ring does not occur.The products from the photodegradation were trans-2-methoxy-6-methyltetrahydropyran (8), methyl hexanoate (10), 6-methyltetrahydropyran-2-one (9), methyl 5-phenylhexanoate (11), 1,7-dimethyl-7-phenyl-6,8-dioxobicyclooctane (13), and 2-methoxy-2-(1-phenyl-1-hydroxyethyl)-6-methyltetrahydropyran (12).The yield of lactone 9 was found to be sensitive to the amount of residual oxygen present during the photolysis.