- BICMAP-rhodium(I)-catalyzed asymmetric 1,4-addition of arylboronic acids to coumarins
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Rhodium(I)-catalyzed asymmetric 1,4-addition of arylboronic acids 2 to coumarins 1 using (S)-BICMAP as a chiral ligand gave the desired 4-arylchroman-2-one derivatives 2 in good yields and with high enantioselectivities (up to 99% ee).
- Mino, Takashi,Miura, Kazuki,Taguchi, Hiroyuki,Watanabe, Kohei,Sakamoto, Masami
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- Palladium Catalyzed Enantioselective Hayashi-Miyaura Reaction for Pharmaceutically Important 4-Aryl-3,4-dihydrocoumarins
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The first palladium-catalyzed asymmetric addition of arylboronic acids to coumarins was successfully established, providing a straightforward asymmetric approach to achieving pharmaceutically important 4-aryl-3,4-dihydrocoumarins. This methodology features easily accessible and bench-stable ligands, a wide substrate scope, mild conditions, and accommodation of electron-withdrawing arylboronic acids.
- Csuk, René,Lai, Jixing,Li, Shengkun,Song, Baoan,Yang, Chen
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supporting information
p. 1329 - 1334
(2022/02/23)
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- Asymmetric Hydroesterification of Diarylmethyl Carbinols
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An efficient asymmetric hydroesterfication of diarylmethyl carbinols is developed for the first time with a Pd-WingPhos catalyst, resulting in a series of chiral 4-aryl-3,4-dihydrocoumarins in excellent enantioselectivities and good yields. The method features mild reaction conditions, a broad substrate scope, use of easily accessible starting materials, and low palladium loadings. A plausible stereochemical model is also proposed with the Pd-WingPhos catalyst. This method has enabled a 4-step asymmetric synthesis of (R)-tolterodine from readily available starting materials.
- Tian, Duanshuai,Xu, Ronghua,Zhu, Jinbin,Huang, Jianxun,Dong, Wei,Claverie, Jerome,Tang, Wenjun
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p. 6305 - 6309
(2021/02/09)
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- Conjugate addition of aryl nucleophiles to α,β-unsaturated cinnamic acid derivatives containing Evans type chiral auxiliaries
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Cinnamides containing oxazolidin-2-one type auxiliaries have been prepared. A novel pathway to chiral 4-aryl-6-methyl-3,4-dihydrocoumrines via the asymmetric conjugate addition of arylmagnesium bromides to these cinnamides is described.
- Leitis, Zigmārs,Lūsis, Viesturs
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p. 843 - 851
(2016/09/02)
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- Catalytic Asymmetric Addition of Meldrum's Acid, Malononitrile, and 1,3-Dicarbonyls to ortho-Quinone Methides Generated In Situ under Basic Conditions
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A new approach to the utilization of highly reactive and unstable ortho-quinone methides (o-QMs) in catalytic asymmetric settings is presented. The enantioselective reactions are catalysed by bifunctional organocatalysts, and the o-QM intermediates are formed in situ from 2-sulfonylalkyl phenols through base-promoted elimination of sulfinic acid. The use of mild Bronsted basic conditions for transiently generating o-QMs in catalytic asymmetric processes is unprecedented, and allows engaging productively in the reactions nucleophiles such as Meldrum's acid, malononitrile and 1,3-dicarbonyls. The catalytic transformations give new and general entries to 3,4-dihydrocoumarins, 4H-chromenes and xanthenones. These frameworks are recurring structures in natural product and medicinal chemistry, as testified by the formal syntheses of (R)-tolterodine and (S)-4-methoxydalbergione from the catalytic adducts.
- Caruana, Lorenzo,Mondatori, Martina,Corti, Vasco,Morales, Sara,Mazzanti, Andrea,Fochi, Mariafrancesca,Bernardi, Luca
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supporting information
p. 6037 - 6041
(2015/04/14)
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- Coumarins from free ortho -hydroxy cinnamates by Heck-Matsuda arylations: A scalable total synthesis of (R)-tolterodine
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Free ortho-hydroxy cinnamate ester derivatives are evaluated in the synthesis of structurally diverse 4-aryl-coumarins via a tandem Heck-Matsuda cyclization reaction. Free phenolic groups were considered incompatible with such a reaction, which usually provide the corresponding diazo dyes. A concise and scalable route employing a ligand-free, Pd-catalyzed Heck-Matsuda arylation under aerobic conditions for the preparation of (R)-Tolterodine in high overall yield and ee is also presented.
- Barancelli, Daniela A.,Salles, Airton G.,Taylor, Jason G.,Correia, Carlos Roque D.
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p. 6036 - 6039
(2013/02/23)
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- Enantioselective synthesis of (S)- and (R)-tolterodine by asymmetric hydrogenation of a coumarin derivative obtained by a Heck reaction
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(Chemical Equation Presented) An efficient and short enantioselective synthesis of (S)- and (R)-tolterodine was performed by asymmetric hydrogenation of a coumarin intermediate, easily obtained by a Heck reaction from inexpensive and commercially available starting materials.
- Ulgheri, Fausta,Marchetti, Mauro,Piccolo, Oreste
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p. 6056 - 6059
(2008/02/10)
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- A process for the preparation of tolterodine and intermediates thereof
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A process for the preparation of 6-methyl-4-(R)-phenyl-chroman-2-one and 6-methyl-4-(S)-phenyl-chroman-2-one, intermediates for the synthesis of tolterodine and its (S) enantiomer, by reaction of 6-methyl-coumarin with phenylboronic acids, esters and derivatives thereof, in the presence of chiral catalysts.
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Page/Page column 8
(2010/02/14)
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- Process for the preparation of tolterodine and intermediates thereof
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A process for the preparation of 6-methyl-4-(R)-phenyl-chroman-2-one and 6-methyl-4-(S)-phenyl-chroman-2-one, intermediates for the synthesis of tolterodine and its (S) enantiomer, by reaction of 6-methyl-coumarin with phenylboronic acids, esters and derivatives thereof, in the presence of chiral catalysts.
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Page/Page column 4
(2010/02/14)
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- ENANTIOSELECTIVE SYNTHESIS OF ENANTIOMERICALLY ENRICHED COMPOUNDS
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Method of preparing an enantiomerically enriched compound of formula (II) comprising enantioselective hydrogenation of a compound of general formula (I): where W, X and Z have the meanings indicated in the description, to give a compound of general formula (II): where W, Y, T and C* have the meanings indicated in the description, in the presence of a catalyst or its suitable precursor based on Rh, Ru or Ir, having an oxidation state of 0, +1 or +2, and containing at least one enantiomerically enriched chiral ligand.
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Page/Page column 9; 10
(2010/02/10)
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