Catalyst‐Enabled Site‐Divergent Stereoselective Michael Reactions: Overriding Intrinsic Reactivity of Enynyl Carbonyl Acceptors

Uraguchi, Daisuke; Shibazaki, Ryo; Tanaka, Naoya; Yamada, Keiichi; Yoshioka, Ken; Ooi, Takashi

doi:10.1002/ange.201800057

Cited by 17 publications

(30 citation statements)

References 55 publications

(24 reference statements)

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“…The reaction of 11i with Ph 2 PCl followed by decomplexation, or after rearrangement upon heating with DABCO, led to the free AMPP* (S P )-13i and (S P )-20i with respective yields of 44% and 58% (Scheme 4c,d). Figure S6 (SI) shows the X-ray structure of the borane complexes (S p )-12i of P-chirogenic AMPP* (S p )-13i, bearing an epimeric o-biphenyl-aminophosphine moiety in relation to (R P )-13f.…”

Section: Resultsmentioning

confidence: 99%

“…35−7.43 (m, 4H), 7.52 (t, J = 7.5 Hz, 1H), 7.57− 7.62 (m, 3H), 7.82−7.85 (m, 2H), 7.91−7.92 (m, 2H). 13 C{1H} NMR (125.8 MHz), CDCl 3 ): δ 9.7 (d, J = 5.5 Hz), 32.6 (d, J = 3.5 Hz), 57.9 (d,J = 9.4 Hz),78.9,125.1,125.5,125.6,125.7,126.7,126.9,127.1,127.5 (d,J = 9.8 Hz),127.6,127.8,127.9,128.1,128.2,128.5,129.3 (d,J = 10.7 Hz), 129.8, 130.3 (d, J = 2.0 Hz), 131.9 (d,J = 9.8 Hz),133.2,133.4,133.7,134.0 (d, J = 9.7 Hz), 134.1, 134.2 (d, J = 7.2 Hz), 134.8 (d, J = 4.0 Hz), 142.6, 144.2 (d, J = 9.9 Hz). 31 P{ 1 H} NMR (202.5 MHz), CDCl 3 ): δ +71.7 (br s).…”

Section: Methodsmentioning

confidence: 99%

“…1 H NMR (300 MHz, CDCl 3 ): δ 0.20−1.60 (m, 6H), 1.22 (d,J = 6.6 Hz,3H),2.27 (d,J = 7.8 Hz,3H),1H),4.69 (s,2H),5.27 (t,J = 9.2 Hz,1H),6.53 (dd,J = 7.4,11.7 Hz,2H),6.63 (d,J = 6.9 Hz,2H),22H),3H). 13 C{ 1 H} NMR (75.5 MHz, CDCl 3 ): δ 15.9, 29.8 (d,J = 4.5 Hz),57.5 (br s),70.1,83.4 (d,J = 9.8 Hz),112.3 (d,J = 4.5 Hz),118.2,118.9,121.2 (d,J = 11.3 Hz),126.8,127.6,127.8,128.0 (d,J = 9.1 Hz),128.2,128.3,128.5 (d,J = 10.6 Hz),128.8,129.6 (d,J = 2.0 Hz),130.4 (d,J = 10.6 Hz),131.0,131.2,131.3 (d,J = 2.0 Hz),131.5,131.7,132.0,132.2 (d,J = 8.3 Hz),…”

Section: (S P )-(−)-N-[(1r2s)-2-(diphenylphosphinitoborane)-1m E Th Y...mentioning

confidence: 99%

“…[α] D 20 = −78.8 (c 1.0, CH 2 Cl 2 ). 1 H NMR (500 MHz, CDCl 3 ): δ 0.50−1.81 (m, 6H), 1.37 (d, J = 6.2 Hz, 3H), 2.32 (s, 6H), 2.33 (d,J = 8.5 Hz,3H),1H), 5.40 (t, J = 9.2 Hz, 3H), 6.64−6.68 (m, 2H), 7.09−7.17 (m, 10H), 7. 26− 7.40 (m, 6H), 7.47−7.54 (m, 3H), 7.73−7.77 (m, 2H).…”

Section: (S P )-(−)-N-[(1r2s)-2-(diphenylphosphinitoborane)-1m E Th Y...mentioning

confidence: 99%

“…26− 7.40 (m, 6H), 7.47−7.54 (m, 3H), 7.73−7.77 (m, 2H). 13 C{ 1 H} NMR (125.8 MHz, CDCl 3 ): δ 16.3, 21.4,29.4 (d,J = 4.5 Hz),57.3 (dd,J = 11.2,8.8 Hz), 83.3 (dd, J = 9.0, 2.5 Hz), 127.8 (d, J = 10.6 Hz), 127.9 (d,J = 11.1 Hz),128.2,128.5 (d,J = 9.2 Hz),128.6,128.7,129.8 (d,J = 34.2 Hz),130.1 (d,J = 10.3 Hz),130.2 (d,J = 1.9 Hz),130.4 (d,J = 20.4 Hz),131.0 (d,J = 11.2 Hz),131.3 (d,J = 2.2 Hz),131.6,131.7,131.8 (d,J = 9.8 Hz),132.1 (d,J = 6.5 Hz),132.7,133.0 (d,J = 1.6 Hz),137.9,138.1 (d,J = 5.9 Hz). 31 P{ 1 H} NMR (202.5 MHz, CDCl 3 ): δ +71.2 (br s), +106.8 (br s).…”

Section: (S P )-(−)-N-[(1r2s)-2-(diphenylphosphinitoborane)-1m E Th Y...mentioning

confidence: 99%

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Design of P-Chirogenic Aminophosphine–Phosphinite Ligands at Both Phosphorus Centers: Origin of Enantioselectivities in Pd-Catalyzed Allylic Reactions

et al. 2020

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We have recently patented an unprecedented stereospecific N→O phosphinyl migration process which transforms P-chirogenic aminophosphines into phosphinites. A fine design of aminophosphine phosphinite ligands (AMPP*) derived from ephedrine and bearing a Pchirogenic center either at the aminophosphine or phosphinite moiety, was performed. The synthesis of AMPP* ligands with P-chirogenic aminophosphine moiety was based on the well-established stereospecific reaction of oxazaphospholidine-borane with organolithium

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: (S P )-(−)-N-[(1r2s)-2-(diphenylphosphinitoborane)-1m E Th Y...mentioning

confidence: 99%

Section: (S P )-(−)-N-[(1r2s)-2-(diphenylphosphinitoborane)-1m E Th Y...mentioning

confidence: 99%

Section: (S P )-(−)-N-[(1r2s)-2-(diphenylphosphinitoborane)-1m E Th Y...mentioning

confidence: 99%

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Design of P-Chirogenic Aminophosphine–Phosphinite Ligands at Both Phosphorus Centers: Origin of Enantioselectivities in Pd-Catalyzed Allylic Reactions

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Stereoselective Construction of (E,Z)‐1,3‐Dienes and Its Application in Natural Product Synthesis

et al. 2020

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The E,Z-configured 1,3-diene unit is a common motif in numerous bioactive natural products. Although several powerful methods are available to produce these motifs with high levels of selectivity, their construction within a complex, polyfunctionalised structure, such as a natural product, requires well-defined strategies to avoid undesirable reactions and low-to-moderate selectivities. The aim of this review is to provide a full account of the stereoselective strategies for building E,Z-configured 1,3-dienes, as well as to highlight selected total syntheses that employ them. 2.3. Heck Reactions 2.4. CÀ H activation reactions 2.5. Ir-Catalysed Olefinations 2.6. Carbonyl Olefination Reactions 2.7. Elimination Strategies 2.8. Double Bond Isomerisation Strategies 2.9. Metathesis Strategies 2.10. Ene-Yne Triple Bond Reduction Strategies 2.11. Organocatalysed 1,6-Michael Additions 3. Applications in Total Synthesis: Selected Examples 4. Conclusion

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Pyrazoleamides in Catalytic Asymmetric Reactions: Recent Advances

et al. 2021

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Pyrazoleamides are a class of compounds which have received significant attention in the last years in asymmetric catalysis as more reactive and practical surrogates of esters or amides. These readily available reagents have served in a variety of diastereo-and enantioselective metal-and organocatalytic transformations, spanning from simple carbon-carbon or carbon-heteroatom bond formation to cascade and rearrangement reactions, to produce valuable classes of heterocyclic compounds. More recently, pyrazoleamides have proved to be pertinent reagents in asymmetric catalysis merged with photoredox catalysis, and in more challenging stereoselective bond-forming reactions, occurring directly from a visible-light activated substrate/catalyst complex without any charge separation. Both strategies enable new activation concepts useful for the production of difficult-to-access intermediates and pharmaceuticals. In this review, an overview of the progress achieved in asymmetric catalytic reactions of pyrazoleamides from 2015 up to middle 2020, is illustrated. Rearrangements of α-Diazo Pyrazoleamides 7. Combined Metal-and Organocatalysis 8. Pyrazoleamides in Visible-Light-Activated Photochemical Reactions 8.1. Merging Visible Light Photoredox Activation with Asymmetric Catalysis 8.2. Stereocontrolled Direct Photoreactions from Electronically Excited State 8.3. Merging HAT Photocatalysis with Chiral Lewis Acid Catalysis 9.

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Catalyst‐Enabled Site‐Divergent Stereoselective Michael Reactions: Overriding Intrinsic Reactivity of Enynyl Carbonyl Acceptors

Cited by 17 publications

References 55 publications

Design of P-Chirogenic Aminophosphine–Phosphinite Ligands at Both Phosphorus Centers: Origin of Enantioselectivities in Pd-Catalyzed Allylic Reactions

Design of P-Chirogenic Aminophosphine–Phosphinite Ligands at Both Phosphorus Centers: Origin of Enantioselectivities in Pd-Catalyzed Allylic Reactions

Stereoselective Construction of (E,Z)‐1,3‐Dienes and Its Application in Natural Product Synthesis

Pyrazoleamides in Catalytic Asymmetric Reactions: Recent Advances

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