4.8 Article

Reactions of a Dilithiomethane with CO and N2O: An Avenue to an Anionic Ketene and a Hexafunctionalized Benzene

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 48, Pages 25281-25285

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202111486

Keywords

carbon monoxide; C-C formation; dilithiomethane; hexasubstituted benzene; ketene cyclotrimerization

Funding

  1. NSERC of Canada
  2. NSERC Canada Research Chair
  3. Killam Foundation
  4. Canada Council for the Arts
  5. DFG
  6. Colin H. Bayley Scholarship
  7. 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

Primary Rating

4.8
Not enough ratings

Secondary Ratings

Novelty
-
Significance
-
Scientific rigor
-
Rate this paper

Recommended

No Data Available
No Data Available