- Palladium-Catalyzed Asymmetric Markovnikov Hydroxycarbonylation and Hydroalkoxycarbonylation of Vinyl Arenes: Synthesis of 2-Arylpropanoic Acids
-
Asymmetric hydroxycarbonylation is one of the most fundamental yet challenging methods for the synthesis of carboxylic acids. Herein, we reported the development of a palladium-catalyzed highly enantioselective Markovnikov hydroxycarbonylation of vinyl arenes with CO and water. A monodentate phosphoramidite ligand L6 plays vital role in the reaction. The reaction tolerates a range of functional groups, and provides a facile and atom-economical approach to an array of 2-arylpropanoic acids including several commonly used non-steroidal anti-inflammatory drugs. The catalytic system has also enabled an asymmetric Markovnikov hydroalkoxycarbonylation of vinyl arenes with alcohols to afford 2-arylpropanates. Mechanistic investigations suggested that the hydropalladation is irreversible and is the regio- and enantiodetermining step, while hydrolysis/alcoholysis is probably the rate-limiting step.
- Guan, Zheng-Hui,Ren, Zhi-Hui,Wang, Yuan,Yang, Hui-Yi,Yao, Ya-Hong,Zou, Xian-Jin
-
supporting information
p. 23117 - 23122
(2021/09/18)
-
- Asymmetric Hydrogenation of α-Substituted Acrylic Acids Catalyzed by a Ruthenocenyl Phosphino-oxazoline-Ruthenium Complex
-
Asymmetric hydrogenation of various α-substituted acrylic acids was carried out using RuPHOX-Ru as a chiral catalyst under 5 bar H2, affording the corresponding chiral α-substituted propanic acids in up to 99% yield and 99.9% ee. The reaction could be performed on a gram-scale with a relatively low catalyst loading (up to 5000 S/C), and the resulting product (97%, 99.3% ee) can be used as a key intermediate to construct bioactive chiral molecules. The asymmetric protocol was successfully applied to an asymmetric synthesis of dihydroartemisinic acid, a key intermediate required for the industrial synthesis of the antimalarial drug artemisinin.
- Li, Jing,Shen, Jiefeng,Xia, Chao,Wang, Yanzhao,Liu, Delong,Zhang, Wanbin
-
p. 2122 - 2125
(2016/06/01)
-
- Ferrocenyl chiral bisphosphorus ligands for highly enantioselective asymmetric hydrogenation via noncovalent ion pair interaction
-
A new class of ferrocenyl chiral bisphosphorus ligand, Wudaphos, was developed, and exhibits excellent ee and activity (ee up to 99%, TON up to 20000) for the asymmetric hydrogenation of both 2-aryl and 2-alkyl acrylic acids through ion pair noncovalent interaction under base free and mild reaction conditions. Well-known anti-inflammatory drugs such as naproxen and ibuprofen together with the intermediate for the preparation of Roche ester and some bioactive compounds were also efficiently obtained with excellent ee. Control experiments were conducted and revealed that the ion pair noncovalent interaction and chain length played important roles.
- Chen, Caiyou,Wang, Heng,Zhang, Zhefan,Jin, Shicheng,Wen, Songwei,Ji, Jianjian,Chung, Lung Wa,Dong, Xiu-Qin,Zhang, Xumu
-
p. 6669 - 6673
(2016/10/31)
-
- Chiral diphosphine ligand in asymmetric hydrogenation thereof and related application of the catalyst in the reaction (by machine translation)
-
The invention discloses a chiral diphosphine ligand based on ferrocene skeleton in asymmetric hydrogenation thereof and related application of the catalyst in the reaction. This kind of novel chiral diphosphine ligand has as the general formula I The structure of the shown, wherein R 1 can be is methyl, phenyl, tert-butyl, hydroxy, etc.. R 2 can be ethyl, phenyl, cyclohexyl, methyl phenyl, tert-butyl, 3,5-dimethyl phenyl, 3,5-di-tert-butyl phenyl, 3,5-di-tert-butyl-4-methoxybenzene, 2,6-dimethoxyphenyl, 2,6-dimethyl phenyl, anthryl. At the same time, two phosphine atom bridged between the can is phenyl, naphthyl, alkyl or the like. At the same time, this invention has disclosed this kind of novel chiral diphosphine ligand synthesis and in preparation of chiral pharmaceutical ibuprofen and a naproxen, and the like. (by machine translation)
- -
-
Paragraph 0104; 0108; 0109
(2016/10/09)
-
- Simultaneous control of regioselectivity and enantioselectivity in the hydroxycarbonylation and methoxycarbonylation of vinyl arenes
-
Using a family of novel mononuclear and dinuclear palladium complexes of phanephos ligands, the simultaneous control of regioselectivity and enantioselectivity in the hydroxycarbonylation and alkoxycarbonylation of styrene derivatives has been realised for the first time. The Royal Society of Chemistry 2013.
- Konrad, Tina M.,Durrani, Jamie T.,Cobley, Christopher J.,Clarke, Matthew L.
-
supporting information
p. 3306 - 3308
(2013/06/05)
-
- Highly enantioselective hydroxycarbonylation and alkoxycarbonylation of alkenes using dipalladium complexes as precatalysts
-
Joined at Pd: Novel palladium catalysts like 1, in which the planar-chiral phosphine acts as a bridging ligand, have been developed. These dimetallic complexes are highly enantioselective catalysts in the hydroxycarbonylation of alkenes, a reaction that has proven problematic over the years. PTSA=para-toluenesulfonic acid. Copyright
- Konrad, Tina M.,Fuentes, Jose A.,Slawin, Alexandra M. Z.,Clarke, Matthew L.
-
supporting information; experimental part
p. 9197 - 9200
(2011/02/28)
-
- Enantioselective synthesis of α-methyl carboxylic acids using a DiTOX chiral auxiliary
-
Five α-methyl carboxylic acids have been prepared with high e.e.s using 1,3-dithiane 1-oxide (DiTOX) units as the stereocontrolling elements and sources of chirality.
- Page, Philip C. Bulman,McKenzie, Michael J.,Allin, Steven M.,Klair, Sukhbinder S.
-
p. 13149 - 13164
(2007/10/03)
-
- Enantioselective synthesis of α-arylpropanoic acids
-
A range of (+)-α-arylpropanoic acids has been prepared in high enantiomeric excesses using 1,3-dithiane 1-oxide (DiTOX) units as the stereocontrolling elements and sources of chirality.
- Page, Philip C.,McKenzie, Michael J.,Buckle, Derek R.
-
p. 2673 - 2676
(2007/10/02)
-