Experimental and Computational Study of the ( Z)-Selective Formation of Trisubstituted Olefins and Benzo-Fused Oxacycles from the Ruthenium-Catalyzed Dehydrative C-H Coupling of Phenols with Ketones

Journal of the American Chemical Society
Hanbin LeeChae S Yi

Abstract

The cationic Ru-H complex was found to be an effective catalyst for the dehydrative C-H coupling of phenols with ketones to form the trisubstituted olefin products. The coupling of phenol with linear ketones led to highly stereoselective formation of the ( Z)-olefin products. The dehydrative coupling of phenol with enones and diones efficiently formed the benzopyrene and related oxacyclic derivatives. The reaction of 3,5-dimethoxyphenol with cyclohexanone-2,2,6,6- d4 showed a significant H/D exchange to both vinyl and α-CH2 positions on the olefin product (72-75% D). A significant carbon isotope effect was observed on the ortho-arene carbon of the olefin product. The free energies of intermediate species for the entire catalytic cycle were successfully computed by using the DFT method. The DFT study revealed that the E/ Z stereoselectivity is a result of the energy difference in the insertion step of ortho-metalated phenol to an enol form of the ketone substrate (ΔΔ E = 9.6 kcal/mol). The coupling method provides a direct catalytic C-H olefination method for ketones to form trisubstituted olefins without employing any reactive reagents or forming any wasteful byproducts.

References

Sep 15, 1988·Physical Review A: General Physics·A D Becke
Jul 19, 2002·Chemical Society Reviews·L Frances van StadenDavid J Ager
Oct 16, 2002·Accounts of Chemical Research·Fumitoshi Kakiuchi, Shinji Murai
Dec 18, 2003·Journal of the American Chemical Society·Daniel T NowlanDaniel A Singleton
Jun 5, 2004·Organic Letters·Eric C Hansen, Daesung Lee
Apr 28, 2005·Journal of the American Chemical Society·Daniel T Nowlan, Daniel A Singleton
Aug 10, 2007·Journal of the American Chemical Society·Daniel H Ess, K N Houk
Nov 2, 2007·Chemical Reviews·Alison B Flynn, William W Ogilvie
Jul 11, 2008·Journal of the American Chemical Society·Daniel H Ess, K N Houk
Sep 18, 2009·Organic Letters·Takuji HatakeyamaMasaharu Nakamura
Jun 15, 2011·Chemical Society Reviews·Joanna Wencel-DelordFrank Glorius
Sep 1, 2012·Chemical Reviews·Percia Beatrice ArockiamPierre H Dixneuf
Jan 16, 2013·Journal of the American Chemical Society·Lauren E RosebrughRobert H Grubbs
Aug 29, 2014·Angewandte Chemie·Dipankar SrimaniDavid Milstein
Apr 28, 2016·Nature·Jacob R LudwigCorinna S Schindler
Apr 13, 2017·Journal of the American Chemical Society·Chuanhu LeiJianrong Steve Zhou
Jul 29, 2017·Journal of the American Chemical Society·Jacob R LudwigCorinna S Schindler
Mar 24, 2018·Chemical Science·Wei WeiChao-Jun Li

❮ Previous
Next ❯

Citations

May 25, 2021·Organic & Biomolecular Chemistry·So Won Youn, Cheon-Gyu Cho
Jun 23, 2021·Organic & Biomolecular Chemistry·Zhiqiong TangLu Liu
Nov 15, 2019·The Journal of Organic Chemistry·Amanda M Spiewak, Daniel J Weix
Dec 30, 2021·Organic Letters·Zheng-Hai Wang, Dong-Hui Wang

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.