Stereoselective alkoxycarbonylation of unactivated C(sp³)–H bonds with alkyl chloroformates via Pd(II)/Pd(IV) catalysis
Abstract
Several examples on Pd-catalysed carbonylation of methyl C(sp^3)–H bonds with gaseous CO via Pd(II)/Pd(0) catalysis have been reported. However, methylene C(sp³)–H carbonylation remains a great challenge, largely due to the lack of reactivity of C–H bonds and the difficulty in CO migratory insertion. Herein, we report the stereoselective alkoxycarbonylation of both methyl and methylene C(sp³)–H bonds with alkyl chloroformates through a Pd(II)/Pd(IV) catalytic cycle. A broad range of aliphatic carboxamides and alkyl chloroformates are compatible with this protocol. In addition, this process is scalable and the directing group could be easily removed under mild conditions with complete retention of configuration.
Additional Information
© 2016 The Author(s). This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ Received: 20 April 2016; Accepted: 12 August 2016; Published online: 28 September 2016. Financial support from the National Basic Research Program of China (2015CB856600) and the NSFC (21572201, 21422206, 21272206) is gratefully acknowledged. We thank Prof. Xueqian Kong from Zhejiang University, China for help with the use of facilities in his lab. Competing financial interests: B.-F.S., G.L. and X.-S.Y. are the co-inventors on a patent application: 'A highly efficient method to the synthesis of aspartate derivatives' CN application number 201610147639.1. The remaining authors declare no competing financial interests.Attached Files
Published - ncomms12901.pdf
Supplemental Material - ncomms12901-s1.pdf
Supplemental Material - ncomms12901-s2.cif
Supplemental Material - ncomms12901-s3.cif
Supplemental Material - ncomms12901-s4.cif
Supplemental Material - ncomms12901-s5.cif
Supplemental Material - ncomms12901-s6.cif
Supplemental Material - ncomms12901-s7.cif
Supplemental Material - ncomms12901-s8.pdf
Files
| Name | Size | Download all |
|---|---|---|
|
md5:246f094ef5b609835b0e22ab22724e16
|
26.1 kB | Download |
|
md5:3cbd4ce37f0a12d24227a9f799d72763
|
22.9 kB | Download |
|
md5:a129b22ab13d1004413e7be0c3a0587a
|
22.3 kB | Download |
|
md5:84cff69b50e0706d2f59ae0525780dd5
|
28.0 kB | Download |
|
md5:4721ac2d3c41d1bdb03f89bcb7158428
|
20.1 kB | Download |
|
md5:76585d3675230b1ba2136e407db74419
|
531.1 kB | Preview Download |
|
md5:62187dedd018c724261ac1404df7ace6
|
840.7 kB | Preview Download |
|
md5:03529a3e2855fd0335f091ae94944a0b
|
23.2 kB | Download |
|
md5:61c3df4ed583040a9116bf74241ab611
|
14.0 MB | Preview Download |
Additional details
- PMCID
- PMC5052708
- Eprint ID
- 71770
- Resolver ID
- CaltechAUTHORS:20161107-114157093
- 2015CB856600
- National Basic Research Program of China
- 21572201
- National Natural Science Foundation of China
- 21422206
- National Natural Science Foundation of China
- 21272206
- National Natural Science Foundation of China
- Created
-
2016-11-07Created from EPrint's datestamp field
- Updated
-
2022-04-14Created from EPrint's last_modified field