Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 48, Pages 25281-25285Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202111486
Keywords
carbon monoxide; C-C formation; dilithiomethane; hexasubstituted benzene; ketene cyclotrimerization
Categories
Funding
- NSERC of Canada
- NSERC Canada Research Chair
- Killam Foundation
- Canada Council for the Arts
- DFG
- Colin H. Bayley Scholarship
- China Scholarship Council
Ask authors/readers for more resources
This study presents a transition metal-free method for synthesizing hexa-substituted benzene derivatives from simple C1 feedstocks, which is viable on a gram scale and allows for the incorporation of C-13 labels. The mechanisms of these reactions are elucidated through extensive density functional theory computations.
Synthesis of value-added products from simple C1 feedstocks is an attractive alternative avenue to traditional fossil fuels. Hexa-substituted benzene derivatives are highly useful molecules but are often challenging to prepare. Herein, we report that the lithium complex [(Ph2P(S))(2)CLi2(THF)](2) 1 reacts with CO lead to C-C bond formation and migration of a Ph2P(S)-fragment affording 2. Subsequent reaction with N2O results in oxidative cleavage of a P-C bond affording [Ph2P(S)OLi(THF)(2)](2) 4 and the anionic ketene-derivative Ph2P(S)CCOLi(THF)(2) 5. Heating 5 prompts cyclotrimerization giving the hexa-substituted benzene derivative [Ph2P(S)CCOLi(THF)(2)](3) 6 regioselectively. This transition metal-free protocol to a hexa-substituted benzene is viable on a gram scale and permits the incorporation of C-13 labels. The mechanisms of these reactions are detailed via extensive DFT computations.
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