skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Rh(I)‐Catalyzed Direct C6−H Arylation of 2‐Pyridones with Aryl Carboxylic Acids
Abstract A Rh(I)‐catalyzed C6‐selective C−H arylation of 2‐pyridones with inexpensive, readily available, safe and structurally diverse aryl carboxylic acids with the aid of a pyridine directing group is developed. This decarbonylative arylation protocol features an easy‐to‐handle catalytic system, and is amenable to diversely substituted 2‐pyridones and aryl carboxylic acids. It allows access to a wide range of C6‐arylated 2‐pyridones, including those that are difficult to prepare using conventional C−H arylation processes. The method tolerates various electron‐neutral, electron‐rich and electron‐deficient functional groups, and affords the products in 41–91% yields. magnified image  more » « less
Award ID(s):
1902509
PAR ID:
10253971
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Synthesis & Catalysis
Volume:
363
Issue:
16
ISSN:
1615-4150
Format(s):
Medium: X Size: p. 3995-4001
Size(s):
p. 3995-4001
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract The direct C−H acyloxylation of polycyclic aromatic hydrocarbons (PAHs) with carboxylic acids as the acyloxylating agents was achieved via the electron‐donor‐acceptor (EDA) complexes between PAHs andN‐iodosuccinimide (NIS). This visible light‐assisted metal‐free C−H acyloxylation reaction provides an easy access to the desired aryl carboxylates from readily available PAHs and aliphatic and aromatic carboxylic acids under mild reaction conditions. magnified image 
    more » « less
  2. Abstract A Rh(II)/Au(I) catalyzed carbene cascade approach for the stereoselective synthesis of diverse spirocarbocycles is described. The cascade reaction involves a rhodium carbene initiatedsp2C−H functionalization followed by a gold catalyzed Conia‐ene cyclization. The cascade reaction accommodates a variety of aryl substituents as well as ring sizes and proceeds with high diastereoselectivity providing access to diverse spirocarbocycles. magnified image 
    more » « less
  3. Abstract The direct formation of aryl C−O bonds via the intramolecular dehydrogenative coupling of a C−H bond and a pendant alcohol represents a powerful synthetic transformation. Herein, we report a method for intramolecular arene C−H etherification via an umpoled alcohol cyclization mediated by an I(III)N‐HVI reagent. This approach provides access to functionalized chromane scaffolds from primary, secondary and tertiary alcohols via a cascade cyclization‐iodonium salt formation, the latter providing a versatile functional handle for downstream derivatization. Computational studies support initial formation of an umpoled O‐intermediate via I(III) ligand exchange, followed by competitive direct and spirocyclization/1,2‐shift pathways. magnified image 
    more » « less
  4. Abstract The diastereodivergent synthesis of bridged 1,2,3,4‐tetrahydroisoquinoline derivatives has been achieved by using appropriate modularly designed organocatalysts (MDOs) that are self‐assembled in situ from amino acids and cinchona alkaloid derivatives. The domino Mannich/aza‐Michael/aldol reaction between (E)‐2‐[2‐(3‐aryl‐3‐oxoprop‐1‐en‐1‐yl)phenyl]acetaldehydes and ethyl or benzyl (E)‐2‐[(4‐methoxyphenyl)imino]acetates catalyzed by MDOs gives two different diastereomers of the desired bridged tetrahydroisoquinolines in good yields and excellent diastereoselectivities (up to 99:1 dr) and enantioselectivities (up to >99%ee). The diastereodivergence was achieved in the aldol reaction step. magnified image 
    more » « less
  5. Abstract We report that treatment of several 2‐diphenylphosphinoimidazoles with Pd(II) salts generates monosubstituted N−H NHC−Pd complexes via insertion into the C−P bond. Removal of the N−H proton in situ leads to anionic (X‐type) or imidazolyl‐Pd complexes that are highly stable and catalytically active, achieving up to 340,000 turnovers at 1 ppm catalyst loading in Suzuki‐Miyaura reactions. DFT‐calculated Tolman electronic parameters for the sterically small ligands suggest that these ligands are significantly more donating than traditional NHCs, which provides a rationale for rapid cross‐coupling catalysis. Excellent reactivity is also demonstrated in Sonogashira reactions. magnified image 
    more » « less