Catalytic Enantioselective Allylation of Ketimines by Using Palladium Pincer Complexes with Chiral Bis(imidazoline)s

Nakamura, Shuichi; Hyodo, Kengo; Nakamura, Masayuki; Nakane, Daisuke; Masuda, Hideki

doi:10.1002/chem.201300685

Cited by 105 publications

(48 citation statements)

References 109 publications

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“…The catalytic enantioselective allylation of isatin ketimines can be readily obtained using trimethoxyallylsilane 207 in the presence of the chiral palladium complex 208 (Scheme ) …”

Section: Spiroheterocyclic Derivativesmentioning

confidence: 99%

Recent Developments in the Stereoselective Synthesis of Nitrogen‐Containing Heterocycles using N‐Acylimines as Reactive Substrates

Marcantoni

Petrini

2016

Adv Synth Catal

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Scheme 3. Enantioselective synthesis of trans-aziridines 8 catalyzed by chiral phosphoric acid 10. Scheme 4. Enantioselective synthesis of trans-aziridines 14. Scheme5.Preparation of chiral aziridines 17. Scheme6.Synthesis of chiral aziridines 20. Scheme 22. Synthesis of chiral 2-pyrrolines 82. Scheme23. Enantioselective synthesis of epi-cytoxazone 89. Scheme 24. Synthesis of the mGluR5modulator 96. Scheme 25. Synthesis of chiral 1,3-oxazolines. Scheme26. Synthesis of chiral imidazolidin-2-one 102. Scheme 27. Enantioselectiven itro-Mannichr eaction.Scheme28. Synthesis of (À)-nutlin-3 111.Scheme29. Synthesis of functionalized tetrahydropyridines. Scheme 32. Synthesis of chiral piperidines 129. Scheme 33. One-pot synthesis of N-formylpiperidines. Scheme34. Synthesis of bicyclic aminal 136. Scheme 39. General synthesis of isatin ketimines. Scheme 40. Asymmetric Staudinger reaction. Scheme41. Synthesis of spirocyclic oxindolo-g-lactams. Scheme 42. Synthesis of methylidenes pirocyclic compounds. Scheme 43. Synthesis of spirooxindolepyrrolines. Scheme44. Synthesis of imidazoline-based spirooxindoles. Scheme 48. Synthesis of spirolactam derivatives. Scheme49. Synthesis of spirooxindolelactams 201. Scheme50. Synthesis of polycyclic spirolactams 203. Scheme 56. Synthesis of chiral spiroazetidin-2-ones 228.

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“…The catalytic enantioselective allylation of isatin ketimines can be readily obtained using trimethoxyallylsilane 207 in the presence of the chiral palladium complex 208 (Scheme ) …”

Section: Spiroheterocyclic Derivativesmentioning

confidence: 99%

Recent Developments in the Stereoselective Synthesis of Nitrogen‐Containing Heterocycles using N‐Acylimines as Reactive Substrates

Marcantoni

Petrini

2016

Adv Synth Catal

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“…1a) 7 . Other disclosures cover highly activated ketimines, including cyclic sulfonylimines and their reaction with potassium allyltrifluoroborates (with Rh-based catalysts) 8, 9 and isatin-derived N -Boc-ketimines and their reaction with allylsilanes (with Pd-based complexes and stoichiometric silver fluoride) 10 . Other approaches involve either enantiomerically pure ketimines 11, 12 or enantiomerically pure allyl reagents 13,14,15 .…”

mentioning

confidence: 99%

Catalytic diastereo- and enantioselective additions of versatile allyl groups to N–H ketimines

et al. 2017

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There are countless biologically active organic molecules that contain one or more N-containing moieties and broadly applicable and efficient catalytic transformations that deliver them diastereo- and/or enantioselectively are much sought after. Various methods for enantioselective synthesis of α-secondary amines are available (e.g., from additions to protected/activated aldimines), but those involving ketimines are much less common. There are no reported additions of carbon-based nucleophiles to unprotected/unactivated (or N-H) ketimines. Here, we report a catalytic, diastereo- and enantioselective three-component strategy for merging an N-H ketimine, a monosubstituted allene and B2(pin)2, affording products in up to 95% yield, >98% diastereoselectivity and >99:1 enantiomeric ratio. Utility of the approach is highlighted by synthesis of the tricyclic core of a class of compounds that have been shown to possess anti-Alzheimer activity. Stereochemical models, developed with the aid of DFT calculations, which account for the observed trends and levels of enantioselectivity are presented.

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“…18 Nakamura et al reported an enantioselective allylation protocol to N-Boc ketimines 20 derived from isatins catalyzed by chiral Pd pincer-type catalyst 21 (Scheme 6). 19 The combined use of allyltrimethoxysilane and silver fluoride was essential for a smooth reaction, affording the allylated products 22 bearing a stereogenic α-tertiary amine on the oxindole core.…”

Section: Ketimines Derived From Isatinsmentioning

confidence: 99%

Recent Advances in Catalytic Asymmetric C–C Bond-Forming Reactions to Ketimines Promoted by Metal-Based Catalysts

Kumagai

Shibasaki

2014

Bulletin of the Chemical Society of Japan

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Recent progress (post-2010) in the field of metal-catalyzed asymmetric CC bond-forming reactions using ketimines as electrophiles is reviewed. Compared with the corresponding aldimines, ketimines generally display less inherent reactivity and the two substituents on the imine carbon hamper prochiral-face-selection for enantioselective reactions. Recent advances with newly developed catalytic systems have resulted in several solutions to these long-standing problems. The construction of tetrasubstituted stereogenic centers is a crucial topic of asymmetric catalysis in the 21st century, and it is becoming increasingly clear that reactions using ketimines as electrophiles become one of the most important routes to access such chemical entities.

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Catalytic Enantioselective Allylation of Ketimines by Using Palladium Pincer Complexes with Chiral Bis(imidazoline)s

Cited by 105 publications

References 109 publications

Recent Developments in the Stereoselective Synthesis of Nitrogen‐Containing Heterocycles using N‐Acylimines as Reactive Substrates

Recent Developments in the Stereoselective Synthesis of Nitrogen‐Containing Heterocycles using N‐Acylimines as Reactive Substrates

Catalytic diastereo- and enantioselective additions of versatile allyl groups to N–H ketimines

Recent Advances in Catalytic Asymmetric C–C Bond-Forming Reactions to Ketimines Promoted by Metal-Based Catalysts

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