Mechanism and Transition-State Structures for Nickel-Catalyzed Reductive Alkyne−Aldehyde Coupling Reactions
The mechanism of nickel-catalyzed reductive alkyne−aldehyde coupling reactions has been investigated using density functional theory. The preferred mechanism involves oxidative cyclization to form the nickeladihydrofuran intermediate followed by transmetalation and reductive elimination. The rate- a...
| Main Authors: | , , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
American Chemical Society (ACS)
2013
|
| Online Access: | http://hdl.handle.net/1721.1/82098 https://orcid.org/0000-0002-8601-7799 |
| _version_ | 1826192067867443200 |
|---|---|
| author | McCarren, Patrick R. Liu, Peng Cheong, Paul Ha-Yeon Jamison, Timothy F. Houk, K. N. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry McCarren, Patrick R. Liu, Peng Cheong, Paul Ha-Yeon Jamison, Timothy F. Houk, K. N. |
| author_sort | McCarren, Patrick R. |
| collection | MIT |
| description | The mechanism of nickel-catalyzed reductive alkyne−aldehyde coupling reactions has been investigated using density functional theory. The preferred mechanism involves oxidative cyclization to form the nickeladihydrofuran intermediate followed by transmetalation and reductive elimination. The rate- and selectivity-determining oxidative cyclization transition state is analyzed in detail. The d → π* back-donation stabilizes the transition state and leads to higher reactivity for alkynes than alkenes. Strong Lewis acids accelerate the couplings with both alkynes and alkenes by coordinating with the aldehyde oxygen in the transition state. |
| first_indexed | 2024-09-23T09:05:47Z |
| format | Article |
| id | mit-1721.1/82098 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T09:05:47Z |
| publishDate | 2013 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/820982022-09-26T10:24:59Z Mechanism and Transition-State Structures for Nickel-Catalyzed Reductive Alkyne−Aldehyde Coupling Reactions McCarren, Patrick R. Liu, Peng Cheong, Paul Ha-Yeon Jamison, Timothy F. Houk, K. N. Massachusetts Institute of Technology. Department of Chemistry Jamison, Timothy F. The mechanism of nickel-catalyzed reductive alkyne−aldehyde coupling reactions has been investigated using density functional theory. The preferred mechanism involves oxidative cyclization to form the nickeladihydrofuran intermediate followed by transmetalation and reductive elimination. The rate- and selectivity-determining oxidative cyclization transition state is analyzed in detail. The d → π* back-donation stabilizes the transition state and leads to higher reactivity for alkynes than alkenes. Strong Lewis acids accelerate the couplings with both alkynes and alkenes by coordinating with the aldehyde oxygen in the transition state. National Science Foundation (U.S.) (CHE-0548209) 2013-11-13T15:09:02Z 2013-11-13T15:09:02Z 2009-04 2009-01 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/82098 McCarren, P. R., Peng Liu, Paul Ha-Yeon Cheong, Timothy F. Jamison, and K. N. Houk. “Mechanism and Transition-State Structures for Nickel-Catalyzed Reductive Alkyne−Aldehyde Coupling Reactions.” Journal of the American Chemical Society 131, no. 19 (May 20, 2009): 6654-6655. https://orcid.org/0000-0002-8601-7799 en_US http://dx.doi.org/10.1021/ja900701g Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) PMC |
| spellingShingle | McCarren, Patrick R. Liu, Peng Cheong, Paul Ha-Yeon Jamison, Timothy F. Houk, K. N. Mechanism and Transition-State Structures for Nickel-Catalyzed Reductive Alkyne−Aldehyde Coupling Reactions |
| title | Mechanism and Transition-State Structures for Nickel-Catalyzed Reductive Alkyne−Aldehyde Coupling Reactions |
| title_full | Mechanism and Transition-State Structures for Nickel-Catalyzed Reductive Alkyne−Aldehyde Coupling Reactions |
| title_fullStr | Mechanism and Transition-State Structures for Nickel-Catalyzed Reductive Alkyne−Aldehyde Coupling Reactions |
| title_full_unstemmed | Mechanism and Transition-State Structures for Nickel-Catalyzed Reductive Alkyne−Aldehyde Coupling Reactions |
| title_short | Mechanism and Transition-State Structures for Nickel-Catalyzed Reductive Alkyne−Aldehyde Coupling Reactions |
| title_sort | mechanism and transition state structures for nickel catalyzed reductive alkyne aldehyde coupling reactions |
| url | http://hdl.handle.net/1721.1/82098 https://orcid.org/0000-0002-8601-7799 |
| work_keys_str_mv | AT mccarrenpatrickr mechanismandtransitionstatestructuresfornickelcatalyzedreductivealkynealdehydecouplingreactions AT liupeng mechanismandtransitionstatestructuresfornickelcatalyzedreductivealkynealdehydecouplingreactions AT cheongpaulhayeon mechanismandtransitionstatestructuresfornickelcatalyzedreductivealkynealdehydecouplingreactions AT jamisontimothyf mechanismandtransitionstatestructuresfornickelcatalyzedreductivealkynealdehydecouplingreactions AT houkkn mechanismandtransitionstatestructuresfornickelcatalyzedreductivealkynealdehydecouplingreactions |