Blog

C-H Arylation of Phenanthrene with Trimethylphenylsilane by Pd/o-Chloranil Catalysis: Computational Studies on the Mechanism, Regioselectivity, and Role of o-Chloranil

Mari Shibata, Hideto Ito,* Kenichiro Itami*
J. Am. Chem. Soc. 2018, 140, 2196–2205. DOI: 10.1021/jacs.7b11260

Tansition-metal-catalyzed C–H arylation of aromatic hydrocarbons represents a useful and ideal method for the production of biaryls and multiarylated aromatic compounds. We have previously reported the palladium-catalyzed direct C–H arylation of polycyclic aromatic hydrocarbons, such as phenanthrene, pyrene, and corannulene with various organosilicon, -borane, and -germanium compounds. In these reactions, o-chloranil proved to be an essential and unique promoter (stoichiometrically as an oxidant) and arylation occurred exclusively at the K-region. Herein, we report our mechanistic investigation of Pd/o-chloranil catalysis in C–H arylation of phenanthrene with trimethylphenylsilane by computational calculations. The results revealed that C–H arylation occurs through a sequence of transmetalation, carbometalation, and trans-β-hydrogen elimination steps. In addition, the triple role of o-chloranil as a ligand, oxidant, and base is also elucidated.

(For other applications of the present mechanistic investigation to homocoupling reaction of aryltrimethylsilanes by Pd/o-cholranil catalytic system, see: Mari Shibata, Hideto Ito,* Kenichiro Itami* Chem. Lett. 201746, 1701–1704. DOI: 10.1246/cl.170723.)。

Related post

  1. The AMOR Arabinogalactan Sugar C…
  2. Laterally π-Extended Dithia[6]he…
  3. Controlling the Circadian Clock …
  4. Chemical synthesis of carbon nan…
  5. Topologically Unique Molecular N…
  6. Thiophene-Based, Radial π-Conjug…
  7. Functionalization of a Simple Di…
  8. Strigolactone receptors in Strig…

Twitter@Itami Lab

Itami Lab Facebook

Instagram@Itami Lab

最近の記事

Flickr@Itamilab

天池先輩からコーヒースープ伴夫妻からのお歳暮です!潤さん、宮村さん、ありがとうございます!!武藤さん、ビールありがとうございます!平賀大都わーいやなさん、あつしさん、ありがとうございます!!だいぶ前だけど、Stripes look #ootdHalloween lookラインを洗う時ですら格好良く。戸谷先生教育実習!imageけいしゅう、誕生日おめでとう!誕生日は英吉家!!3年生に名古屋ぼろ勝ちアピール中!!アリシア卒業おめでとう女子会!
PAGE TOP