论文目录 | |
| ACKNOWLEDGEMENTS | 第1-10页 |
| ABSTRACT | 第10-15页 |
| 1. INTRODUCTION | 第15-56页 |
| 1.1. ASYMMETRIC CONSTRUCTION OF ALL-CARBON QUATERNARY STEREOCENTERS | 第16-28页 |
| 1.1.1. Asymmetric conjugate addition | 第17-19页 |
| 1.1.2. Asymmetric Diels-Alder reactions | 第19-21页 |
| 1.1.3. Intramolecular Heck reactions | 第21-22页 |
| 1.1.4. Cyclopropanation reactions | 第22-24页 |
| 1.1.5. Semipinacol rearrangement | 第24-26页 |
| 1.1.6. Claisen rearrangement | 第26-27页 |
| 1.1.7. 1,2-Migration reactions | 第27-28页 |
| 1.2. ENANTIOSELECTIVE CONSTRUCTION OF ΑLPA-TERTIARY ALCOHOL | 第28-36页 |
| 1.2.1. Addition of carbon nucleophiles to ketones | 第29-33页 |
| 1.2.2. Asymmetric dihydroxylation of 1,1-disubstituted alkenes | 第33-34页 |
| 1.2.3. Asymmetric epoxidation of 1,1-disubstituted alkenes | 第34-35页 |
| 1.2.4. Kinetic resolution and desymmetrization | 第35-36页 |
| 1.3. ENANTIOSELECTIVE CONSTRUCTION OF ΑLPA-TERTIARY AMINE | 第36-44页 |
| 1.3.1. Addition of carbon nucleophile to ketimine | 第37-41页 |
| 1.3.1.1. Enantioselective allylation of ketimine | 第38页 |
| 1.3.1.2. Asymmetric Mannich-type reactions of ketimine | 第38-39页 |
| 1.3.1.3. Asymmetric Strecker-type reactions of ketimine | 第39-40页 |
| 1.3.1.4. Addition of organoboron reagents | 第40-41页 |
| 1.3.2. Asymmetric α-amination of tertiary carbonyl compounds | 第41-42页 |
| 1.3.3. Aza-Claisen rearrangement reactions | 第42-43页 |
| 1.3.4. Asymmetric Wacker-type cyclization | 第43-44页 |
| 1.4. CONSTRUCTION OF QUATERNARY STEREOCENTERS VIA ASYMMETRIC ALLYLIC SUBSTITUTIONREACTIONS | 第44-56页 |
| 1.4.1 Asymmetric allylic substitution reactions with tertiary carbon nucleophile | 第44-47页 |
| 1.4.2 Construction of quaternary stereocenters via asymmetric decarboxylative allylation | 第47-50页 |
| 1.4.3 Asymmetric allylic substitution of 1,1- or 3,3-disubstituted allyl donors | 第50-52页 |
| 1.4.4 Construction of quaternary stereocenters via asymmetric allylic substitution of vinylepoxide | 第52-53页 |
| 1.4.5. New synthetic strategy for the construction of quaternary stereocenters via Pd-catalyzedasymmetric decarboxylative cycloaddition | 第53-56页 |
| 2. RESULTS AND DISCUSSION | 第56-94页 |
| 2.1. PALLADIUM-CATALYZED DC REACTIONS OF VECS WITH FORMALDEHYDE: ENANTIOSELECTIVECONSTRUCTION OF TERTIARY VINYLGLYCOLS | 第56-72页 |
| 2.1.1 Synthesis of substituted vinyl ethylene carbonates (VECs) | 第57-61页 |
| 2.1.2 Conditions optimization for Pd-catalyzed DC of VECs with formaldehyde | 第61-66页 |
| 2.1.3 Substrate scope of Pd-catalyzed DC of VECs with formaldehyde | 第66-68页 |
| 2.1.4 Conformation of the absolute configuration of 89a, 89o, and 90b | 第68-69页 |
| 2.1.5 Stereochemical outcome of the reaction | 第69-70页 |
| 2.1.6 Synthetic application | 第70-71页 |
| 2.1.7 Conclusion | 第71-72页 |
| 2.2. PALLADIUM-CATALYZED ENANTIOSELECTIVE DC REACTIONS OF VECS WITH ISOCYANATES | 第72-85页 |
| 2.2.1. Optimization conditions | 第73-78页 |
| 2.2.1.1. Ligand effect for the Pd-catalyzed DC reactions of VEC 88á with isocyanate 92a | 第73-76页 |
| 2.2.1.2. Pd-catalyzed DC reactions of VEC 88á with various isocyanates 92 | 第76页 |
| 2.2.1.3. Pd-catalyzed DC reactions of Me-VEC 88o with isocyanate 92a | 第76-78页 |
| 2.2.2. Substrate scope for the Pd-catalyzed DC reactions of VECs 88 with isocyanate 92a | 第78-80页 |
| 2.2.3. Confirmation of the absolute configuration | 第80页 |
| 2.2.4. Stereochemical outcome of the reaction | 第80-82页 |
| 2.2.5. Synthetic utility of the process | 第82-84页 |
| 2.2.5.1. Gram-scale syntheses | 第82-83页 |
| 2.2.5.2. Synthesis of β-substituted β-vinylglycinols | 第83页 |
| 2.2.5.3. Formal synthesis of MK-0731 | 第83-84页 |
| 2.2.6. Conclusion | 第84-85页 |
| 2.3. PALLADIUM-CATALYZED ASYMMETRIC DC REACTIONS OF VECS WITH MICHAEL ACCEPTORS: CONSTRUCTION OF VICINAL QUATERNARY STEREOCENTERS | 第85-94页 |
| 2.3.1. Conditions optimization for Pd-catalyzed DC of VEC 88a with Michael acceptor 100a..85 | 第85-87页 |
| 2.3.2. Substrate Scope for Pd-catalyzed DC reactions of VECs 88 with Michael acceptor 100 | 第87-91页 |
| 2.3.3. Synthetic utility of the reaction process | 第91-92页 |
| 2.3.4. Conclusion | 第92-94页 |
| 3. CONCLUSION | 第94-96页 |
| 4. EXPERIMENTAL | 第96-176页 |
| 4.1. General experimental details | 第96-97页 |
| 4.2. General procedure for the synthesis of quaternary VECs | 第97-107页 |
| 4.3. Representative General Procedures for the Pd-catalyzed Asymmetric Decarboxylative Cycloaddition of VECs with Formaldehyde | 第107-119页 |
| 4.4. Representative General Procedures for the Pd-catalyzed Asymmetric Decarboxylative Cycloaddition of Ph-VEC (88a) with other Aldehydes | 第119-122页 |
| 4.5. General procedures for the deprotection of 1,3-dioxolanes 89 | 第122-124页 |
| 4.6. Representative general procedures for Pd-catalyzed asymmetric decarboxylative cycloaddition of VECs 88á with isocyanates 92 | 第124-129页 |
| 4.7. Representative general procedures for Pd-catalyzed asymmetric decarboxylative cycloaddition of 4-substituted VECs 88 with 2-mthoxyphenylisocyanates 92a | 第129-141页 |
| 4.8. Procedures for the deprotection of 93 to β-substituted β-vinylglycinols 94 | 第141-143页 |
| 4.9. Procedures for the hydrolysis of 94 | 第143-144页 |
| 4.10. Procedures for the hydrogenation of 94 to 95 | 第144-145页 |
| 4.11. Procedures for the synthesis of MK-0731 | 第145-148页 |
| 4.12. Representative general procedures for Pd-catalyzed decarboxylative cycloaddition of VECs 88 with 2-benzylidenemalononitrile 100a | 第148-154页 |
| 4.13. Representative general procedures for Pd-catalyzed decarboxylative cycloaddition of VECs 88a with substituted methylenemalononitrile 100 | 第154-159页 |
| 4.14. Representative general procedures for Pd-catalyzed decarboxylative cycloaddition of Ph-VEC 88a with different activated Michael acceptors 102 | 第159-164页 |
| 4.15. Procedures for scale-up transformation and elaboration of 101ae to corresponding amino acid 105 | 第164-166页 |
| 4.16. X-ray Crystallographic data | 第166-170页 |
| 4.17. Density Functional Theory (DFT) calculation for the reaction of 88a and formaldehyde | 第170-172页 |
| 4.18. Density Functional Theory (DFT) calculation for the reaction of 88á, and 88o with isocyante 92a | 第172-176页 |
| 5. REFERENCES | 第176-199页 |
| ABSTRACT IN CHINESE | 第199-201页 |
| PUBLICATION LIST | 第201页 |
