Catalytic Asymmetric Synthesis

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 (η 6‐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 η 5C 5Me 5(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 N 2P 2‐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 , N Scheme 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 15.54. Intramolecular asymmetric reductive amination (ARA).Scheme 15.55. Intermolecular asymmetric reductive amination (ARA).

16 Chapter 16Figure 16.1. Selection of bioactive and pharmaceutically active compounds co...Scheme 16.1. Enantioselective addition of Grignard reagents to aldehydes cat...Scheme 16.2. Cu(I)‐catalyzed enantioselective addition of Grignard reagent t...Scheme 16.3. Arylation of ketones catalyzed by Ti/Binol (a) [21] and Mg/Bino...Scheme 16.4. Rh(I)‐catalyzed enantioselective addition of arylboroxines to k...Scheme 16.5. Rh‐catalyzed enantioselective arylation of keto esters (a) [31]...Scheme 16.6. Ni‐catalyzed enantioselective arylation of ketones with organob...Scheme 16.7. Cu(I)‐catalyzed enantioselective intramolecular addition of ary...Scheme 16.8. Catalytic enantio‐ and diastereoselective synthesis of adjacent...Scheme 16.9. Addition of allyl and allenyl organoboron reagents to ketones, ...Scheme 16.10. Enantioselective allylation of ketones containing a tri‐, a di...Scheme 16.11. Enantioselective allylboration of ketones catalyzed by 1,16‐di...Scheme 16.12. Zn(II)‐catalyzed enantioselective allenylation of ketones [44]...Scheme 16.13. Catalytic enantioselective propargylation of trifluoromethyl k...Scheme 16.14. Catalytic enantioselective propargylation of aryl ketones [47]...Scheme 16.15. Catalytic enantioselective arylation of ketones with organotit...Figure 16.2. Selection of bioactive and pharmaceutically active compounds co...Scheme 16.16. Cu(I)‐catalyzed enantioselective alkylation of silyl/aryl (a) ...Scheme 16.17. Rh(I)‐catalyzed enantioselective arylation of acyclic (a) [62]...Scheme 16.18. Rh(I)‐catalyzed enantioselective additions of arylboronic acid...Scheme 16.19. Rh(I)‐catalyzed enantioselective arylation of isatin‐derived N...Scheme 16.20. Pd(II)‐catalyzed enantioselective arylation of cyclic α‐ketimi...Scheme 16.21. Pd(II)‐catalyzed enantioselective arylation cyclic ketimines [...Scheme 16.22. Pd(II)‐catalyzed enantioselective arylation of trifluoromethyl...Scheme 16.23. Pd(II)‐catalyzed enantioselective arylation of isatin‐derived ...Scheme 16.24. Pd(II)‐catalyzed enantioselective arylation of cyclic seven‐me...Scheme 16.25. Ni(II)‐catalyzed enantioselective arylations (a) [94] and alke...Scheme 16.26. Co‐catalyzed enantioselective allylation of cyclic ketimines [...Scheme 16.27. Cu(I)‐catalyzed diastereoselective and enantioselective additi...Scheme 16.28. Catalytic Cu(I)‐catalyzed synthesis of C‐tertiary amine from u...Scheme 16.29. Alkenyl‐substituted N‐heteroaromatics as Michael acceptors in ...Scheme 16.30. Lewis acid enabled Cu(I)‐catalyzed conjugate additions to unac...Scheme 16.31. Cu(I)‐catalyzed enantioselective addition of Grignard reagents...Scheme 16.32. Cu(I)‐catalyzed enantioselective addition of Grignard reagents...Scheme 16.33. Cu(I)‐catalyzed enantioselective addition of Grignard reagents...Scheme 16.34. Cu(I)‐catalyzed enantioselective reactions with N‐heteroaromat...Scheme 16.35. Catalytic enantioselective conjugate additions of organozinc r...Scheme 16.36. Selection of successful chiral ligands developed for catalytic...Scheme 16.37. Cu(I)‐catalyzed conjugate additions of organozinc reagents to ...Scheme 16.38. Cu(I)‐catalyzed conjugate additions of organozinc reagents to ...Scheme 16.39. Selection of successful chiral ligands developed for catalytic...Scheme 16.40. Selection of successful chiral ligands developed for catalytic...Scheme 16.41. Cu(I)‐catalyzed conjugate additions of organozirconium reagent...Scheme 16.42. Cu(I)‐catalyzed conjugate additions of organozirconium reagent...Scheme 16.43. Rh(I)‐catalyzed conjugate additions of organoboron reagents to...Scheme 16.44. Rh(I)‐catalyzed conjugate additions of boronic acids to α,β‐un...Scheme 16.45. Rh(I)‐catalyzed conjugate addition of boronic acids to cyclic ...Scheme 16.46. Rh(I)‐catalyzed conjugate addition of organoboron reagent to a...Scheme 16.47. Copper(I)‐catalyzed conjugate addition of arylboron reagents t...Scheme 16.48. Rh(I)‐catalyzed conjugate addition of arylboronic acids to var...Scheme 16.49. Rh(I)‐catalyzed enantioselective synthesis of 3,3‐diaryl‐SPINO...Scheme 16.50. Selection of successful chiral ligands developed for catalytic...Scheme 16.51. Rh(I)‐catalyzed enantioselective synthesis of chiral indole (a...Scheme 16.52. Cu(I)‐carbene catalyzed conjugate additions to α,β‐unsaturated...Scheme 16.53. Rh(I)‐catalyzed enantioselective arylation of sulfolene (a) [2...Scheme 16.54. Rh(I)‐catalyzed enantioselective arylation of α,β‐unsaturated ...