Journal
CHEMICAL SCIENCE
Volume 11, Issue 32, Pages 8476-8481Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d0sc03220d
Keywords
-
Categories
Funding
- National Natural Science Foundation of China [21973052, 21933008, 21602116, 91745101]
- National Science AMP
- Technology Fundamental Resource Investigation Program of China [2018FY201200]
Ask authors/readers for more resources
C-O bond cleavage is often a key process in defunctionalization of organic compounds as well as in degradation of natural polymers. However, it seldom occurs regioselectively for different types of C-O bonds under metal-free mild conditions. Here we report a facile chemo-selective cleavage of the alpha-C-O bonds in alpha-carboxy ketones by commercially available pinacolborane under the catalysis of diazaphosphinane based on a mechanism switch strategy. This new reaction features high efficiency, low cost and good group-tolerance, and is also amenable to catalytic deprotection of desyl-protected carboxylic acids and amino acids. Mechanistic studies indicated an electron-transfer-initiated radical process, underlining two crucial steps: (1) the initiator azodiisobutyronitrile switches originally hydridic reduction to kinetically more accessible electron reduction; and (2) the catalytic phosphorus species upconverts weakly reducing pinacolborane into strongly reducing diazaphosphinane.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available