Catalytic Asymmetric Synthesis. Группа авторов
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synthesis from β‐haloamines.Scheme 13.19. Asymmetric α‐fluorination of aldehydes.Scheme 13.20. Asymmetric α‐fluorination of α‐substituted aldehydes.Scheme 13.21. Selective α‐fluorination of ketones.Scheme 13.22. Asymmetric fluorination of 1,3‐dicarbonyl compounds.Scheme 13.23. NHC‐catalyzed oxidative α‐fluorination of aldehydes.Scheme 13.24. Fluorination of 2‐substituted (E)‐cinnamamides.Scheme 13.25. Preparation of chiral α‐chloroaldehydes from enals.Scheme 13.26. Three‐step synthesis of chiral α‐chloroketones from enaminones...Scheme 13.27. Asymmetric vicinal dichlorination of styrenes, allylic alcohol...Scheme 13.28. Asymmetric chlorocyclization reactions.Scheme 13.29. Desymmetrizing chlorination of diolefins using chiral sulfide ...Scheme 13.30. Kinetic resolution of allylic amides through an intramolecular...Scheme 13.31. Asymmetric chlorination of α‐substituted β‐ketoesters.Scheme 13.32. Asymmetric chloroetherification of enones catalyzed by chiral Scheme 13.33. Asymmetric chloroamination of unsaturated olefins catalyzed by...Scheme 13.34. Kinetic resolution of tetrahydropyridine allyl chlorides.Scheme 13.35. Asymmetric bromoamination of chalcones with NBS catalyzed by c...Scheme 13.36. Asymmetric haloazidation of allylic alcohols.Scheme 13.37. Asymmetric haloazidation of allylic alcohols.Scheme 13.38. Enantioselective bromoaminocyclization of tosylcarbamate deriv...Scheme 13.39. Asymmetric organocatalytic bromolactonization of α‐exo‐methyle...Scheme 13.40. Asymmetric organocatalytic bromohydroxylation of aryl olefins ...Scheme 13.41. Asymmetric organocatalytic 5‐exo and 6‐endo‐bromolactonization...Figure 13.1. BINAP ligands used in bromofunctionalization reactions.Scheme 13.42. Enantioselective bromolactonization of deactivated olefinic ac...Scheme 13.43. Organocatalysts used in the asymmetric α‐bromination of aldehy...Scheme 13.44. Mechanism of cyclization by iodoamination or iodolactonization...Scheme 13.45. Asymmetric iodoamination reaction developed by Jacobsen’s grou...Scheme 13.46. Iodoaminocyclization procedure developed by Tripathi and Mukhe...Scheme 13.47. Effects of KBr vs KI additive in the iodoaminocyclization reac...Scheme 13.48. TRIP‐catalyzed enantioselective addition of NIS to enecarbamat...Scheme 13.49. Formation of chiral cyclic ureas described by Struble and cowo...Scheme 13.50. Iodoamination with concomitant trapping of CO2.Scheme 13.51. Enantioselective iodolactonizations catalyzed by tri‐Zn comple...Scheme 13.52. Desymmetrization of diallylacetic acid derivatives catalyzed b...Scheme 13.53. Desymmetrization reaction described by the Johnston group.
14 Chapter 14Scheme 14.1. Enzymatic kinetic resolution (R isomer is considered the fast‐r...Scheme 14.2. Enzymatic repeated kinetic resolution.Scheme 14.3. Parallel kinetic resolution (PKR).Scheme 14.4. Dynamic kinetic resolution (DKR) general scheme.Scheme 14.5. Deracemization procedures for obtaining optically active compou...Scheme 14.6. Desymmetrization of prochiral or meso‐compounds.Scheme 14.7. Schematic stereopreference of lipases.Scheme 14.8. Examples of hydrolytic KRs catalyzed by lipases. (a) Stereosele...Scheme 14.9. Some examples of lipase‐catalyzed KRs via O‐ and N‐acylations. ...Scheme 14.10. KRs via oxygen insertion in C–H bonds employing oxidoreductase...Scheme 14.11. DKRs employing metal catalysts for the substrate racemization....Scheme 14.12. Biocatalyzed DKRs employing transaminases and alcalases. (a) D...Scheme 14.13. Some examples of DYRKR for the synthesis of optically active c...Scheme 14.14. Some examples of deracemizations catalyzed by enzymes for the ...Scheme 14.15. Parallel kinetic resolutions catalyzed by oxidative biocatalys...Scheme 14.16. Desymmetrization of prochiral compounds catalyzed by different...Scheme 14.17. Synthesis of valuable compounds in enzymatic desymmetrizations...Scheme 14.18. Transaminase‐catalyzed desymmetrization procedures. (a) Synthe...Scheme 14.19. Multienzymatic systems for the preparation of valuable chiral ...Scheme 14.20. Multicatalytic systems combining enzymes and organocatalysts f...
15 Chapter 15Scheme 15.1. Rhodium‐catalyzed AH of functionalized alkenes with the general...Figure 15.1. Rhodium‐catalyzed AH of some less common substrates.Scheme 15.2. AH of cyclic α‐dehydro ketones and synthesis of β,β‐diaryl‐α‐am...Scheme 15.3. AH of α‐formyl and conjugated enamides.Scheme 15.4. Hydrogenation of itaconic acid analogues.Figure 15.2. Rhodium‐catalyzed AH of less conventional enamides.Scheme 15.5. AH of other enamides: conjugated, β‐aryl bicyclic, and tetrasub...Scheme 15.6. AH of enol ester derivatives: 1‐alkyl vinyl esters and aryl vin...Scheme 15.7. Preparation of 1,2‐difunctional products by rhodium‐catalyzed A...Scheme 15.8. AH involving supramolecular interactions between the catalyst a...Scheme 15.9. Hydrogenative desymmetrization reactions and kinetic resolution...Scheme 15.10. Rhodium‐catalyzed AH of α‐ or β‐trifluoromethyl‐substituted ac...Scheme 15.11. Preparation of acyclic and cyclic sulfones by rhodium‐catalyze...Scheme 15.12. Cobalt‐catalyzed AH of α‐N‐acyl acrylates and enamides with ne...Scheme 15.13. AH of α‐N‐acyl acrylates and enamides with cationic cobalt(I) ...Scheme 15.14. Nickel‐catalyzed AH of α,β‐unsaturated esters and α‐N‐acyl acr...Scheme 15.15. AH of alkenes without any specific requirement in terms of the...Scheme 15.16. Iridium‐catalyzed AH of α,β‐unsaturated acid derivatives: male...Scheme 15.17. Iridium‐catalyzed AH of exocyclic compounds.Scheme 15.18. Iridium‐catalyzed AH of (poly)cyclic compounds.Scheme 15.19. Iridium‐catalyzed hydrogenation and spiroketalization of bis(2...Scheme 15.20. AH of alkenylboronic esters and chloro alkenyl boronic esters....Scheme 15.21. Iridium‐catalyzed AH of sulfones and fluorine‐substituted olef...Scheme 15.22. Ruthenium‐catalyzed AH of isocoumarines and benzothiophene dio...Scheme 15.23. Asymmetric hydrogenation of (E)‐2‐methyl‐2‐stilbene (S72) usin...Figure 15.3. Chiral P,N‐ligands bearing heterocycles other than oxazolines u...Figure 15.4. Chiral phosphinoamines and phosphinites as P,N‐ligands used in ...Figure 15.5. Phosphinoferrocenyl ligands and a P‐stereogenic pyridyl‐dihydro...Figure 15.6. Phosphites as phosphorus donors in P,N‐ligands for the iridium‐...Figure 15.7. Chiral P,O‐ and P,S‐ligands used in the iridium‐catalyzed asymm...Figure 15.8. Chiral C,N‐ligands with N‐heterocyclic carbenes reported for th...Scheme 15.24. Hydrogenation of trisubstituted unfunctionalized alkenes and d...Scheme 15.25. Examples of asymmetric hydrogenation of 1,1‐disubstituted alke...Scheme 15.26. Examples of asymmetric hydrogenation of tetrasubstituted olefi...Scheme 15.27. Rh‐catalyzed hydrogenation of unfunctionalized olefins.Scheme 15.28. Co‐catalyzed hydrogenation of unfunctionalized olefins.Scheme 15.29. Synthesis of an intermediate (P93) of hepaindole alkaloids by ...Scheme 15.30. Selected examples of AH of bicyclic ketones by Boehringer‐Inge...Scheme 15.31. Selected examples of AH by Ohkuma’s rutenabicyclic catalysts C...Scheme 15.32. Initial (η6‐Arene)/N‐Ts‐diamine ruthenium catalysts (C16). Sel...Figure 15.9. Mohar’s catalyst for ATH.Figure 15.10. Other ruthenium catalysts: bimetallic, cyclometallated, and wi...Figure 15.11. Chiral η5 C5Me5 (Cp*)‐rhodium and iridium complexes.Scheme 15.33. Rhodium‐catalyzed AHs of ketones with P‐stereogenic bisphosphi...Scheme 15.34. Rhodium‐catalyzed AH of 2‐pyridine ketones.Scheme 15.35. Rhodium‐catalyzed AH of aryl perfluoroalkyl ketones and triflu...Scheme 15.36. Selected examples of AH of alkyl aryl ketones by the iridium c...Scheme 15.37. AH of aryl ketones by iridium‐SpiroPAP complexes.Scheme 15.38. AH of alkyl ketones by iridium‐SpiroPNP complexes.Scheme 15.39. Selected examples of the AH of simple ketones by iridium compl...Scheme 15.40. Iridium‐catalyzed AH of diaryl ketones.Figure 15.12. Structures of Iridium complexes with chiral NHC employed in th...Figure 15.13. Open‐chain N2P2‐ligand and macrocyclic ligands used in the pre...Figure 15.14. Iron catalysts for the ATH or AH of ketones.Scheme 15.41. AH of aromatic ketones using iron complex C45.Figure 15.15. Initial manganese complexes for AH and ATH.Scheme 15.42. AH catalyzed by a manganese complex.Scheme 15.43. Selected examples of asymmetric hydrogenation of isoquinolines...Scheme 15.44. Hydrogenation of pyrimidines and benzoxazinones with Ir‐P,P ca...Scheme 15.45. Hydrogenation of 1‐pyrrolines and pyridinium salts with Ir‐P,NScheme 15.46. AH of various N‐aromatic heterocycles with ruthenium arene‐dia...Scheme 15.47. Ruthenium‐catalyzed AH of quinoxalines with an NHC ligand.Scheme 15.48. Biomimetic asymmetric hydrogenation of benzoxazinones.Scheme 15.49. Cobalt‐ and nickel‐catalyzed AH of sulfonyl ketimines and benz...Scheme 15.50. Iron‐catalyzed ATH and AH of phosphinyl imines.Scheme 15.51. Cooperative iron‐catalyzed asymmetric hydrogenation of N‐pheny...Scheme 15.52. Asymmetric hydrogenation of N‐aryl and N‐alkyl imines.Scheme 15.53. Asymmetric hydrogenation of O‐alkyl oximes.Scheme