Efficient Enantioselective Synthesis of 3-Aminochroman Derivatives Through Ruthenium-Synphos Catalyzed Asymmetric Hydrogenation

Wu, Zi Ping; Ayad, Tahar; Ratovelomanana‐Vidal, Virginie

doi:10.1021/ol201786q

Cited by 44 publications

(14 citation statements)

References 41 publications

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“…Among the most successful reports, Ratovelomanana et al. published the synthesis of 3‐aminochromanes with enantioselectivities up to 96% using Ru‐diphosphine catalysts . A more recent report showed similar high enantioselectivities in the reduction of enamides derived from 2‐tetralones ( ee s up to 96%) and enamides derived from 3‐chromanones ( ee s in the range 94–98%), using a Rh‐diphosphine catalysts .…”

Section: Resultsmentioning

confidence: 99%

Alternatives to Phosphinooxazoline (t‐BuPHOX) Ligands in the Metal‐Catalyzed Hydrogenation of Minimally Functionalized Olefins and Cyclic β‐Enamides

et al. 2017

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This studyp resents an ew serieso fr eadily accessible iridium-and rhodium-phosphite/oxazoline catalytic systems that can efficiently hydrogenate,f or the first time,b othm inimally functionalized olefins and functionalized olefins (62 examples in total) in high enantioselectivities( eesu pt o> 99%) and conversions. Thep hosphite-oxazoline ligands,w hich are readily available in only two synthetic steps,a re derived from previous privileged 4-alkyl-2-[2-(diphenylphosphino)phenyl]-2-oxazoline (PHOX) ligands by replacing the phosphinemoiety by ab iaryl phosphite group and/or the introductiono famethylene spacer between the oxazoline and the phenylr ing. The modular design of the ligands hasgiven us the opportunity not only to overcome the limitations of the iridium-PHOX catalytic systems in the hydrogenation of minimally functionalized Z-olefins and 1,1-disubstitutedo lefins, but also to expand theiru se to unfunctionalized olefins containing other challenging scaffolds (e.g.,e xocyclic benzofused andt riaryl-substitutedo lefins) anda lso to olefinsw ith poorly coor-dinativeg roups (e.g., a,b-unsaturated lactams,l actones,a lkenylboronic esters, etc.) with enantioselectivities typically > 95% ee. Moreover, both enantiomers of the hydrogenation product could be obtained by simply changing the configuration of the biaryl phosphite moiety.R emarkably, the new catalytic systems also provided excellent enantioselectivities (up to 99% ee)i nt he asymmetric hydrogenation of another challengingc lass of olefins -t he functionalized cyclic b-enamides.A gain, both enantiomers of the reduceda midesc ould be obtained by changing the metal from Ir to Rh. We also demonstrated that environmentally friendly propylene carbonate can be used with no loss of enantioselectivity.A nothera dvantage of the new ligands over the PHOX ligands is that the best ligands are derived from the affordable (S)-phenylglycinolr ather than from the expensive (S)-tert-leucinol.

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Section: Resultsmentioning

confidence: 99%

Alternatives to Phosphinooxazoline (t‐BuPHOX) Ligands in the Metal‐Catalyzed Hydrogenation of Minimally Functionalized Olefins and Cyclic β‐Enamides

et al. 2017

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“…We next extended the Ru‐catalyzed hydrogenation reaction of trisubstituted enamides to access oxygen‐containing heterocycles, such as chroman derivatives,14 which possess significant biological properties 15. Particularly, 3‐aminochroman scaffolds are numerous structural elements in clinical candidates for psychiatric disorders, such as the selective agonists at 5‐HT 1A receptors Robazaltan (NAD‐299)16 and Alnespirone (+)‐S20499 17.…”

Section: Asymmetric Hydrogenation (Ah)mentioning

confidence: 99%

Transition‐Metal‐Catalyzed Asymmetric Hydrogenation and Transfer Hydrogenation: Sustainable Chemistry to Access Bioactive Molecules

Ayad

Phansavath

Ratovelomanana‐Vidal

2016

The Chemical Record

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Over the last few decades, the development of new and highly efficient synthetic methods to obtain chiral compounds has become an increasingly important and challenging research area in modern synthetic organic chemistry. In this account, we review recent work from our laboratory toward the synthesis of valuable chiral building blocks through transition-metal-catalyzed asymmetric hydrogenation and transfer hydrogenation of C=O, C=N and C=C bonds. Application to the synthesis of biologically relevant products is also described.

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“…7 In 2011, we reported an atom economical and clean process for the synthesis of 3-aminochroman derivatives through cationic Ru-SYNPHOS-catalysed enantioselective hydrogenation of trisubstituted enamides (scheme 2). 8 Initial experiments revealed that the nature of the amide moiety and the substitution pattern in the aromatic ring exerted influence on the stereocontrol, while hydrogen pressure and reaction temperature did not significantly affect the stereochemical outcome. For this process, polar solvents tend to provide higher enantioselectivities than non-polar ones, with methanol being the optimum.…”

Section: Ru-catalysed Asymmetric Hydrogenation Of Trisubstituted Enammentioning

confidence: 99%

DIFLUORPHOS and SYNPHOS in asymmetric catalysis: Synthetic applications

et al. 2014

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Enantiomerically pure diphosphines play an important role in various homogeneous metalcatalyzed asymmetric reactions. Over the last few years, our group has been involved in the design and synthesis of atropisomeric ligands named SYNPHOS and DIFLUORPHOS with complementary stereoelectronic properties. This paper shows the high catalytic performances of DIFLUORPHOS, SYNPHOS and SYNPHOS analogues for some C-H and CC bond forming processes as well as for the synthesis of biorelevant targets.

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Efficient Enantioselective Synthesis of 3-Aminochroman Derivatives Through Ruthenium-Synphos Catalyzed Asymmetric Hydrogenation

Cited by 44 publications

References 41 publications

Alternatives to Phosphinooxazoline (t‐BuPHOX) Ligands in the Metal‐Catalyzed Hydrogenation of Minimally Functionalized Olefins and Cyclic β‐Enamides

Alternatives to Phosphinooxazoline (t‐BuPHOX) Ligands in the Metal‐Catalyzed Hydrogenation of Minimally Functionalized Olefins and Cyclic β‐Enamides

Transition‐Metal‐Catalyzed Asymmetric Hydrogenation and Transfer Hydrogenation: Sustainable Chemistry to Access Bioactive Molecules

DIFLUORPHOS and SYNPHOS in asymmetric catalysis: Synthetic applications

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