Addition of a carbene catalyst to indole aryl aldehyde activates a remote δ-sp2 carbon for protonation and formal [4+2] reaction
The addition of a carbene catalyst to an indole aryl aldehyde leads to the activation of a remote sp2 carbon that is five atoms away from the catalyst. The unsaturated Breslow intermediate formed between the catalyst and substrate undergoes an internal redox reaction and remote carbon protonation to...
| Main Authors: | , , , , , |
|---|---|
| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2020
|
| Subjects: | |
| Online Access: | https://hdl.handle.net/10356/137753 |
| _version_ | 1826111571795902464 |
|---|---|
| author | Zheng, Pengcheng Wu, Shuquan Mou, Chengli Xue, Wei Jin, Zhichao Chi, Robin Yonggui |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Zheng, Pengcheng Wu, Shuquan Mou, Chengli Xue, Wei Jin, Zhichao Chi, Robin Yonggui |
| author_sort | Zheng, Pengcheng |
| collection | NTU |
| description | The addition of a carbene catalyst to an indole aryl aldehyde leads to the activation of a remote sp2 carbon that is five atoms away from the catalyst. The unsaturated Breslow intermediate formed between the catalyst and substrate undergoes an internal redox reaction and remote carbon protonation to generate an analogous azolium vinyl enolate intermediate. Subsequent [4+2] reaction with cyclic imine substrates eventually affords multicyclic pyridoindoles as nearly single diastereomers with excellent enantioselectivities. |
| first_indexed | 2024-10-01T02:52:56Z |
| format | Journal Article |
| id | ntu-10356/137753 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T02:52:56Z |
| publishDate | 2020 |
| record_format | dspace |
| spelling | ntu-10356/1377532023-02-28T19:28:14Z Addition of a carbene catalyst to indole aryl aldehyde activates a remote δ-sp2 carbon for protonation and formal [4+2] reaction Zheng, Pengcheng Wu, Shuquan Mou, Chengli Xue, Wei Jin, Zhichao Chi, Robin Yonggui School of Physical and Mathematical Sciences Science::Chemistry::Organic chemistry Carbene Catalyst Breslow Intermediate The addition of a carbene catalyst to an indole aryl aldehyde leads to the activation of a remote sp2 carbon that is five atoms away from the catalyst. The unsaturated Breslow intermediate formed between the catalyst and substrate undergoes an internal redox reaction and remote carbon protonation to generate an analogous azolium vinyl enolate intermediate. Subsequent [4+2] reaction with cyclic imine substrates eventually affords multicyclic pyridoindoles as nearly single diastereomers with excellent enantioselectivities. NRF (Natl Research Foundation, S’pore) ASTAR (Agency for Sci., Tech. and Research, S’pore) MOE (Min. of Education, S’pore) Accepted version 2020-04-13T07:38:04Z 2020-04-13T07:38:04Z 2019 Journal Article Zheng, P., Wu, S., Mou, C., Jin, Z., & Chi, R. Y. (2019). Addition of a carbene catalyst to indole aryl aldehyde activates a remote δ-sp2 carbon for protonation and formal [4+2] reaction. Organic Letters, 21(13), 5026-5029. doi:10.1021/acs.orglett.9b01624 1523-7060 https://hdl.handle.net/10356/137753 10.1021/acs.orglett.9b01624 31199655 2-s2.0-85067946714 13 21 5026 5029 en Organic Letters This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organic Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.orglett.9b01624 application/pdf |
| spellingShingle | Science::Chemistry::Organic chemistry Carbene Catalyst Breslow Intermediate Zheng, Pengcheng Wu, Shuquan Mou, Chengli Xue, Wei Jin, Zhichao Chi, Robin Yonggui Addition of a carbene catalyst to indole aryl aldehyde activates a remote δ-sp2 carbon for protonation and formal [4+2] reaction |
| title | Addition of a carbene catalyst to indole aryl aldehyde activates a remote δ-sp2 carbon for protonation and formal [4+2] reaction |
| title_full | Addition of a carbene catalyst to indole aryl aldehyde activates a remote δ-sp2 carbon for protonation and formal [4+2] reaction |
| title_fullStr | Addition of a carbene catalyst to indole aryl aldehyde activates a remote δ-sp2 carbon for protonation and formal [4+2] reaction |
| title_full_unstemmed | Addition of a carbene catalyst to indole aryl aldehyde activates a remote δ-sp2 carbon for protonation and formal [4+2] reaction |
| title_short | Addition of a carbene catalyst to indole aryl aldehyde activates a remote δ-sp2 carbon for protonation and formal [4+2] reaction |
| title_sort | addition of a carbene catalyst to indole aryl aldehyde activates a remote δ sp2 carbon for protonation and formal 4 2 reaction |
| topic | Science::Chemistry::Organic chemistry Carbene Catalyst Breslow Intermediate |
| url | https://hdl.handle.net/10356/137753 |
| work_keys_str_mv | AT zhengpengcheng additionofacarbenecatalysttoindolearylaldehydeactivatesaremotedsp2carbonforprotonationandformal42reaction AT wushuquan additionofacarbenecatalysttoindolearylaldehydeactivatesaremotedsp2carbonforprotonationandformal42reaction AT mouchengli additionofacarbenecatalysttoindolearylaldehydeactivatesaremotedsp2carbonforprotonationandformal42reaction AT xuewei additionofacarbenecatalysttoindolearylaldehydeactivatesaremotedsp2carbonforprotonationandformal42reaction AT jinzhichao additionofacarbenecatalysttoindolearylaldehydeactivatesaremotedsp2carbonforprotonationandformal42reaction AT chirobinyonggui additionofacarbenecatalysttoindolearylaldehydeactivatesaremotedsp2carbonforprotonationandformal42reaction |