Catalytic Asymmetric Synthesis

5 Chapter 5 Figure 5.1 Some “standard” peptide catalysts applied to two or more asymmetr... Scheme 5.1 Poly(amino acid)‐catalyzed asymmetric Michael addition. Scheme 5.2 Polyalanine‐catalyzed asymmetric epoxidation (Juliá–Colonna epoxi... Scheme 5.3 Proline‐catalyzed asymmetric Robinson annulation (Hajos–Parrish‐E... Scheme 5.4 Proline‐catalyzed asymmetric cross aldol reaction. Scheme 5.5 Stereochemical outcome for the peptide‐catalyzed asymmetric cross... Scheme 5.6 Combinatorial approach for screening of peptide catalyst for cros...Scheme 5.7 One‐pot sequential reactions including peptide‐catalyzed asymmetr...Scheme 5.8 Peptide‐catalyzed kinetic resolution of planar chiral ansa cyclop...Scheme 5.9 Peptide‐catalyzed kinetic resolution of aldols via enantiomer dis...Scheme 5.10 Peptide‐catalyzed diastereo‐/enantioselective nitro Michael addi...Scheme 5.11 Peptide‐catalyzed stereoselective nitro Michael addition of alde...Figure 5.2 Structure of diastereo‐/enantioselective nitro Michael adducts; (...Scheme 5.12 Peptide‐catalyzed anti ‐diastereoselective and enantioselective n...Scheme 5.13 Peptide‐catalyzed asymmetric α‐amination of aldehydes.Scheme 5.14 Peptide‐catalyzed asymmetric Michael addition of 2‐nitropropane ...Scheme 5.15 Peptide‐catalyzed asymmetric hydride conjugate addition to enals...Scheme 5.16 Asymmetric conjugate additions catalyzed by turn‐helix peptides;...Scheme 5.17 Combinatorial approach for screening of peptide catalyst for Mic...Scheme 5.18 Peptide‐catalyzed asymmetric Michael addition of boronic acids t...Scheme 5.19 Peptide‐catalyzed diastereo‐/enantioselective formation of three...Scheme 5.20 Enantiodivergent Michael addition using peptide catalysts having...Scheme 5.21 Peptide‐catalyzed enantioselective Michael addition of malonate ...Scheme 5.22 (a) Peptide‐catalyzed asymmetric Michael addition of carbon nucl...Scheme 5.23 Tandem Michael addition and asymmetric α‐oxyamination of an enal...Scheme 5.24 Divergence in enantioselectivity for catalytic asymmetric epoxid...Figure 5.3 (a) Possible reaction intermediate for Juliá‐Colonna epoxidation....Scheme 5.25 Polyleucine‐catalyzed asymmetric cyanosilylation.Scheme 5.26 Kinetic resolution in the hydrolysis of activated esters by pept...Scheme 5.27 Asymmetric hydrocyanation catalyzed by a cyclic dipeptide.Scheme 5.28 Peptide‐catalyzed kinetic resolution in the acylation of seconda...Scheme 5.29 Combinatorial approach for screening of peptide catalyst for acy...Scheme 5.30 Peptide‐catalyzed enantio‐ or regiodifferentiating reaction in t...Scheme 5.31 Peptide‐catalyzed acylative desymmetrization of a bisphenol‐type...Scheme 5.32 Peptide‐catalyzed site‐selective acylation of a glycoside.Figure 5.4 Site selectivity for the peptide‐catalyzed derivatization of natu...Scheme 5.33 Peptide‐catalyzed acylative kinetic resolution of secondary thio...Scheme 5.34 Peptide‐catalyzed monoacylative kinetic resolution of trans ‐cycl...Scheme 5.35 Peptide‐catalyzed monoacylative desymmetrization of alkane‐1,2‐d...Scheme 5.36 Peptide‐catalyzed asymmetric Dakin–West reaction.Scheme 5.37 Peptide‐catalyzed phosphorylative desymmetrization of a myo ‐inos...Figure 5.5 Site selectivity for the peptide‐catalyzed phosphorylation of tei...Scheme 5.38 Peptide‐catalyzed sulfonylative desymmetrization of a myo ‐inosit...Scheme 5.39 Peptide‐catalyzed site‐selective derivatization of a polyol comp...Scheme 5.40 Peptide/proline‐cocatalyzed asymmetric Morita–Baylis–Hillman rea...Scheme 5.41 Peptide‐catalyzed asymmetric conjugate addition of azide.Scheme 5.42 Catalytic cycle for oxidation mediated by Asp‐containing peptide...Scheme 5.43 Peptide‐catalyzed asymmetric epoxidation of allylic carbamates....Scheme 5.44 Peptide‐catalyzed site‐/enantioselective epoxidation of farnesol...Scheme 5.45 Peptide‐catalyst‐controlled site‐/enantioselective Beayer–Villig...Scheme 5.46 Peptide‐catalyst‐controlled N‐oxidative desymmetrization of dipy...Scheme 5.47 Peptide‐catalyzed N‐Oxidation of conformationally dynamic substr...Scheme 5.48 Peptide‐catalyzed methanolytic dynamic kinetic resolution of oxa...Scheme 5.49 Peptide‐catalyzed asymmetric synthesis of axially chiral bipheny...Scheme 5.50 Peptide‐catalyzed asymmetric synthesis of axially chiral arylami...Scheme 5.51 Peptide‐catalyzed enantioselective synthesis of 3‐arylquinazolin...Scheme 5.52 Peptide‐catalyzed asymmetric synthesis of chiral biaryls by frag...Scheme 5.53 Peptide‐catalyzed asymmetric hydrocyanation of imines by cyclic ...Scheme 5.54 Peptide‐catalyzed asymmetric Michael addition of prochiral nucle...Scheme 5.55 Peptide‐catalyzed atroposelective formation of two‐axis terpheny...Scheme 5.56 Enantioselective Rauhut–Currier reactions promoted by protected ...Scheme 5.57 Enantioselective vinylcyclopropane ring‐opening/cycloaddition ca...Scheme 5.58 Photo‐driven deracemization of urea derivative promoted by a com...Scheme 5.59 Catalytic asymmetric epoxidation of alkenes mediated by trifluor...Scheme 5.60 Peptide‐catalyzed ring‐opening desymmetrization of epoxide.Scheme 5.61 Peptide‐catalyzed acylative kinetic resolution of secondary alco...Scheme 5.62 Peptide‐catalyzed asymmetric bromolaconization.Scheme 5.63 Catalytic oxidation by flavin‐conjugated peptide; (a) sulfoxidat...Scheme 5.64 TEMPO‐conjugated peptoid‐catalyzed oxidative kinetic resolution ...Scheme 5.65 Asymmetric reduction of quinoline derivatives catalyzed by a pep...Scheme 5.66 Reductive kinetic resolution of imines catalyzed by a peptide wi...Scheme 5.67 Enantioselective Baeyer‐Villiger oxidation controlled by a pepti...Scheme 5.68 Atroposelective cyclodehydration leading to axially chiral benzi...Scheme 5.69 Diastereodivergent construction P (III) chiral center from phosph...Scheme 5.70 (a) Pyridine‐conjugated peptide‐catalyzed asymmetric aza‐MBH rea...Scheme 5.71 Site‐selective acylation using peptide catalyst with DMAP‐type s...Scheme 5.72 Peptide‐catalyzed enantioselective transamination of pyruvate....Scheme 5.73 Asymmetric reactions catalyzed by a peptide having thiazolium si...Scheme 5.74 Asymmetric cathodic reduction on polyvaline‐coated graphite elec...Scheme 5.75 Asymmetric anodic sulfoxidation on polyvaline‐coated Pt electrod...

6 Chapter 6Figure 6.1. General structural features of NHCs.Figure 6.2. Early development of benzoin and related reactions via acyl anio...Figure 6.3. Reactions of enals with ketones and aldehydes. (a) NHC‐Catalyzed...Figure 6.4. Reactions of enals with imines, ketimines, and Michael acceptors...Figure 6.5. Reactions of enals involving NHC‐bound enolate intermediates. (a...Figure 6.6. Activation of enals under oxidative NHC catalysis. (a) Generatio...Figure 6.7. NHC‐catalyzed reactions of α‐functionalized aldehydes. (a) Bode’...Figure 6.8. α‐Carbon activation of stable carboxylic esters.Figure 6.9. β‐sp 2‐Carbon activation of α,β‐unsaturared carboxylic esters....Figure 6.10. γ‐Carbon activation of α,β‐unsaturared carboxylic esters.Figure 6.11. NHC‐catalyzed β‐activation of carboxylic esters. (a) Chi’s NHC‐...Figure 6.12. NHC‐catalyzed activation of ketenes. (a) NHC‐catalyzed Stauding...Figure 6.13. NHC‐catalyzed activation of sulfonylimines. (a) Hou’s NHC‐catal...Figure 6.14. NHC‐catalyzed umpolung of imines.Figure 6.15. NHC‐catalyzed activation of remote nitrogen atoms.Figure 6.16. NHC‐catalyzed β‐alkylations of Michael acceptors.Figure 6.17. Biomimetic NHC‐catalyzed oxidations of aldehydes.Figure 6.18. NHC‐catalyzed reductive β,β‐coupling of nitroalkenes. (a) Chi’s...Figure 6.19. NHC‐catalyzed reductive coupling of nitrobenzyl bromides.Figure 6.20. Enantioselective β‐hydroxylation of enals via SET processes.Figure 6.21. NHC‐catalyzed alkylation of aldehydes via SET process. (a) NHC‐...Figure 6.22. NHC‐catalyzed SET difunctionalization of olefins.Figure 6.23. Synergistic Ru‐photoredox/NHC catalysis. (a) Ye’s NHC/photoredo...Figure 6.24. Photoredox and carbene catalysis for the generation of ketones....Figure 6.25. Photoenolization/Diels–Alder reaction of acid fluorides.Figure 6.26. NHC‐catalyzed amidation of unactivated esters. (a) NHC‐catalyze...Figure 6.27. Activation of esters and ketones by NHC as Brønsted base. (a) N...Figure 6.28. Michael additions catalyzed by NHCs through non‐covalent pathwa...Figure 6.29. NHC as Brønsted base catalyzed Michael additions. (a) Scheidt’s...Figure 6.30. Early researches on cooperative NHC/Pd catalysis. (a) Hamada’s ...Figure 6.31. NHC/Pd dual‐catalyzed reactions of aldehydes. (a) Liu’s Pd‐NHC ...Figure 6.32. NHC/Pd dual catalyzed asymmetric coupling reactions. (a) NHC/Pd...Figure 6.33. NHC/Pd dual catalyzed umpolung 1,4‐addition.Figure 6.34. NHC/Cu dual‐catalyzed activation of alkynes as enolate equivale...Figure 6.35. NHC/Cu dual‐catalyzed enantioselective [3+3] and [3+4] annulati...Figure 6.36. Kinetic resolution of aziridines enabled by NHC/Cu dual catalys...Figure 6.37. NHC/Au dual‐catalyzed enantioselective annulation reactions....Figure 6.38. NHC/Ir dual‐catalyzed [3+2] and [4+2] annulations. (a) NHC/Ir d...Figure 6.39. NHC/Lewis acid dual‐catalyzed annulation with homoenolates.Figure 6.40. NHC/Lewis acid dual‐catalyzed reactions. (a) NHC/Lewis acid dua...Figure 6.41. A switched reaction pathway enabled by NHC/Lewis acid dual cata...Figure 6.42. Early cooperative catalytic strategies of NHCs and Brønsted aci...Figure 6.43. NHC/Brønsted acid dual‐catalyzed β‐protonation of enals. (a) Sc...Figure 6.44. NHC/thiourea dual‐catalyzed construction of spirocyclic structu...Figure 6.45. Cooperative catalysis of NHCs with other catalysts. (a) Youn’s ...Figure 6.46. Cooperative catalysis of NHCs and HOBt.Figure 6.47. Kinetic resolution of secondary and tertiary alcohols. (a) Suzu...Figure 6.48. Kinetic resolution of alcohols and phenols. (a) Yamada’s NHC‐ca...Figure 6.49. NHC‐catalyzed kinetic resolution of amines.Figure 6.50. NHC‐catalyzed kinetic resolution of imines. (a) Chi’s NHC‐catal...Figure 6.51. NHC‐catalyzed DKR of functionalized ketones. (a) Bode’s NHC‐cat...Figure 6.52. NHC‐catalyzed DKR of esters and pyranones. (a) Chi’s DKR of α,α...Figure 6.53. Acylative desymmetrization of diols. (a) Rovis’s NHC‐catalyzed ...Figure 6.54. Acylative desymmetrization of biphenols. (a) Chi’s NHC‐catalyze...Figure 6.55. Desymmetrization through benzoin and Stetter reactions. (a) Ema...Figure 6.56. Desymmetrization of 1,4‐dienes and 1,3‐diketones. (a) Fang’s NH...Figure 6.57. Total synthesis of (−)‐seragakinone A.Figure 6.58. Formal synthesis of (±)‐platensimycin.Figure 6.59. Total synthesis of roseophilin.Figure 6.60. Total synthesis of Maremycin B.Figure 6.61. Total synthesis of Yohimbine alkaloids.Figure 6.62. Total synthesis of defucogilvocarcins E, M, and V.Figure 6.63. Synthesis of BCDEF ring analogue of fredericamycin A.Figure 6.64. Total synthesis of (−)‐Δ 9‐tetrahydrocannabinol.Figure 6.65. Total synthesis of (+)‐dactylolide.