Asymmetric Induction in C-Alkylation of Tropane-Derived Enamines: Congruence Between Computation and Experiment
Quantum chemical studies of C-ethylation of 1-methyl- and 1,4,4-trimethyl-tropane-derived enamines predict good (89:11 er, B3LYP) and high (98:2 er, B3LYP) levels, respectively, of asymmetric induction in the resulting α-alkylated aldehydes. The non-racemic tropanes were synthesized using Mannich cy...
| 主要な著者: | , , , , , , , , |
|---|---|
| フォーマット: | Journal article |
| 出版事項: |
American Chemical Society
2017
|
| _version_ | 1826270097829789696 |
|---|---|
| author | Li, Y Jackson, K Charlton, A Le Neve-Foster, B Khurshid, A Rudy, H Thompson, A Paton, R Hodgson, D |
| author_facet | Li, Y Jackson, K Charlton, A Le Neve-Foster, B Khurshid, A Rudy, H Thompson, A Paton, R Hodgson, D |
| author_sort | Li, Y |
| collection | OXFORD |
| description | Quantum chemical studies of C-ethylation of 1-methyl- and 1,4,4-trimethyl-tropane-derived enamines predict good (89:11 er, B3LYP) and high (98:2 er, B3LYP) levels, respectively, of asymmetric induction in the resulting α-alkylated aldehydes. The non-racemic tropanes were synthesized using Mannich cyclization strategies (Robinson-Schöpf and by way of a Davistype N-sulfinyl amino bisketal, respectively), and ethylation of the derived enamines was found to support the predicted sense and magnitude of asymmetric induction (81:19 er and 95:5 er, respectively). A comparison of several computational methods highlights the robustness of predicted trends in enantioselectivity, enabling theory to guide synthesis. |
| first_indexed | 2024-03-06T21:35:31Z |
| format | Journal article |
| id | oxford-uuid:461fb802-676c-418d-a0e3-b0b4aeb85a77 |
| institution | University of Oxford |
| last_indexed | 2024-03-06T21:35:31Z |
| publishDate | 2017 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | oxford-uuid:461fb802-676c-418d-a0e3-b0b4aeb85a772022-03-26T15:11:52ZAsymmetric Induction in C-Alkylation of Tropane-Derived Enamines: Congruence Between Computation and ExperimentJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:461fb802-676c-418d-a0e3-b0b4aeb85a77Symplectic Elements at OxfordAmerican Chemical Society2017Li, YJackson, KCharlton, ALe Neve-Foster, BKhurshid, ARudy, HThompson, APaton, RHodgson, DQuantum chemical studies of C-ethylation of 1-methyl- and 1,4,4-trimethyl-tropane-derived enamines predict good (89:11 er, B3LYP) and high (98:2 er, B3LYP) levels, respectively, of asymmetric induction in the resulting α-alkylated aldehydes. The non-racemic tropanes were synthesized using Mannich cyclization strategies (Robinson-Schöpf and by way of a Davistype N-sulfinyl amino bisketal, respectively), and ethylation of the derived enamines was found to support the predicted sense and magnitude of asymmetric induction (81:19 er and 95:5 er, respectively). A comparison of several computational methods highlights the robustness of predicted trends in enantioselectivity, enabling theory to guide synthesis. |
| spellingShingle | Li, Y Jackson, K Charlton, A Le Neve-Foster, B Khurshid, A Rudy, H Thompson, A Paton, R Hodgson, D Asymmetric Induction in C-Alkylation of Tropane-Derived Enamines: Congruence Between Computation and Experiment |
| title | Asymmetric Induction in C-Alkylation of Tropane-Derived Enamines: Congruence Between Computation and Experiment |
| title_full | Asymmetric Induction in C-Alkylation of Tropane-Derived Enamines: Congruence Between Computation and Experiment |
| title_fullStr | Asymmetric Induction in C-Alkylation of Tropane-Derived Enamines: Congruence Between Computation and Experiment |
| title_full_unstemmed | Asymmetric Induction in C-Alkylation of Tropane-Derived Enamines: Congruence Between Computation and Experiment |
| title_short | Asymmetric Induction in C-Alkylation of Tropane-Derived Enamines: Congruence Between Computation and Experiment |
| title_sort | asymmetric induction in c alkylation of tropane derived enamines congruence between computation and experiment |
| work_keys_str_mv | AT liy asymmetricinductionincalkylationoftropanederivedenaminescongruencebetweencomputationandexperiment AT jacksonk asymmetricinductionincalkylationoftropanederivedenaminescongruencebetweencomputationandexperiment AT charltona asymmetricinductionincalkylationoftropanederivedenaminescongruencebetweencomputationandexperiment AT lenevefosterb asymmetricinductionincalkylationoftropanederivedenaminescongruencebetweencomputationandexperiment AT khurshida asymmetricinductionincalkylationoftropanederivedenaminescongruencebetweencomputationandexperiment AT rudyh asymmetricinductionincalkylationoftropanederivedenaminescongruencebetweencomputationandexperiment AT thompsona asymmetricinductionincalkylationoftropanederivedenaminescongruencebetweencomputationandexperiment AT patonr asymmetricinductionincalkylationoftropanederivedenaminescongruencebetweencomputationandexperiment AT hodgsond asymmetricinductionincalkylationoftropanederivedenaminescongruencebetweencomputationandexperiment |