Transition-Metal-Free C-H Hydroxylation of Carbonyl Compounds.

@article{Chaudhari2017TransitionMetalFreeCH,
  title={Transition-Metal-Free C-H Hydroxylation of Carbonyl Compounds.},
  author={Moreshwar Bhagwan Chaudhari and Yogesh B. Sutar and Shreyas Malpathak and Anirban Hazra and Boopathy Gnanaprakasam},
  journal={Organic letters},
  year={2017},
  volume={19 13},
  pages={
          3628-3631
        }
}
Transition metal and reductant free α-C(sp3)-H hydroxylation of carbonyl compounds are reported. This method is promoted by commercially available inexpensive KO-t-Bu and atmospheric air as an oxidant at room temperature. This unified strategy is also very facile for hydroxylation of various carbonyl compound derivatives to obtain quaternary hydroxyl compounds in excellent yield. A preliminary mechanistic investigation, supported by isotope labeling and computational studies, suggests the… 
41 Citations

Figures and Tables from this paper

Transition-Metal Free Chemoselective Hydroxylation and Hydroxylation-Deuteration of Heterobenzylic Methylenes.
TLDR
By employing this method, active pharmaceutical ingredients carbinoxamine and doxylamine were synthesized in two steps in moderate yields by using a KOBu-t/DMSO/air system.
Directed Hydroxylation of sp2 and sp3 C-H Bonds Using Stoichiometric Amounts of Cu and H2O2.
TLDR
A synthetic protocol for the regioselective hydroxylation of sp2 and sp3 C-H bonds using a directing group, stoichiometric amounts of Cu and H2O2 is reported, which allows for a wide array of aromatic ketones and aldehydes to be oxidation in the carbonyl γ-position with remarkable yields.
Reductant-Free Aerobic Hydroxylation of Isoquinoline-1,3(2 H,4 H)-dione Derivatives.
Base-catalyzed efficient hydroxylation of isoquinoline-1,3(2 H,4 H)-diones with air under transition-metal-free and reductant-free conditions was established. This methodology is essentially mild and
Ligand-Free Ru-Catalyzed Direct sp3 C-H Alkylation of Fluorene Using Alcohols.
TLDR
The sp3 C-H alkylation of 9H-fluorene using alcohol and Ru-catalyst via borrowing hydrogen concept has been described, allowing primary and secondary alcohols to be employed as non-hazardous and greener alkylating agents with the formation of environmentally benign water as a by-product.
Aerobic Direct Dioxygenation of Terminal/Internal Alkynes to form α-Hydroxyketones by Fe Porphyrin Catalyst.
TLDR
A new synthetic method is reported for the preparation of α-hydroxyketones by the dioxygenation of alkynes, affording unsymmetrical α-Hydroxy ketones that are difficult to obtain by any reported dIOxygenations of unsaturated C-C bonds.
C(sp3)-H hydroxylation of fluorenes, oxindoles and benzofuranones with a Mg(NO3)2-HP(O)Ph2 oxidation system.
  • Cheng Hu, Gang Hong, Limin Wang
  • Chemistry, Biology
    Organic chemistry frontiers : an international journal of organic chemistry
  • 2019
A novel oxidation system in which magnesium nitrate [Mg(NO3)2] is used as an oxidant in the presence of diphe-nylphosphine oxide [HP(O)Ph2] permits the C(sp3)-H hydroxylation of fluorenes, oxindoles,
Halogen-bonded iodonium ion catalysis: a route to α-hydroxy ketones via domino oxidations of secondary alcohols and aliphatic C-H bonds with high selectivity and control.
TLDR
A domino synthesis of α-hydroxy ketones has been developed from benzylic secondary alcohols employing catalytic iodonium ions stabilized by DMSO and the spectroscopic evidence establishes the possibility of formation of a stable halogen-bonded adduct between D MSO and iod onium ions.
Visible-light-mediated iodine-catalyzed α-hydroxylation of α-methylene ketones under aerobic conditions
TLDR
Visible light, in combination with the molecular iodine catalyst-mediated α-hydroxylation of α-methylenes ketones, has been developed and shows exclusive selectivity toward methylene ketones.
Direct Aerobic α-Hydroxylation of Arylacetates for the Synthesis of Mandelates.
Aerobic α-hydroxylation of α-methylene esters has proven challenging due to overoxidation and hydrolysis of the materials. In this article, KOtBu-promoted TBAB-catalyzed α-hydroxylation of
...
...

References

SHOWING 1-10 OF 44 REFERENCES
Highly efficient C-H hydroxylation of carbonyl compounds with oxygen under mild conditions.
TLDR
A transition-metal-free Cs2 CO3 -catalyzed α-hydroxylation of carbonyl compounds with O2 as the oxygen source is described and is highly efficient and highly selective for tertiary C(sp(3) )H bond cleavage.
A dinuclear palladium catalyst for α-hydroxylation of carbonyls with O2.
TLDR
A chemo- and regioselective α-hydroxylation reaction of carbonyl compounds with molecular oxygen as oxidant is reported, inspired by discovery and mechanism evaluation of previously unknown Pd(III)-Pd( III) complexes.
Aerobic Direct C(sp2)-H Hydroxylation of 2-Arylpyridines by Palladium Catalysis Induced with Aldehyde Auto-Oxidation
TLDR
A Pd-catalyzed direct C–H hydroxylation of 2-arylpyridines using molecular oxygen (O2) as the sole oxidant and offers an easy access to a broad range of substituted 2-(pyridin-2-yl)phenols in good isolated yields.
Chemoselective oxidative C(CO)-C(methyl) bond cleavage of methyl ketones to aldehydes catalyzed by CuI with molecular oxygen.
TLDR
This method is applicable to a wide range of aromatic and aliphatic methyl ketones and chemoselectively produces aldehydes, accompanied by the release of hydrogen (H2 ) and carbon dioxide (CO2 ) as by-products.
TEMPO-catalyzed aerobic oxygenation and nitrogenation of olefins via C═C double-bond cleavage.
  • Teng Wang, N. Jiao
  • Chemistry, Biology
    Journal of the American Chemical Society
  • 2013
TLDR
A novel TEMPO-catalyzed aerobic oxygenation and nitrogenation of hydrocarbons via C═C double-bond cleavage using molecular oxygen as the terminal oxidant and oxygen-atom source by metal-free catalysis under mild conditions is disclosed.
Factors That Control C-C Cleavage versus C-H Bond Hydroxylation in Copper-Catalyzed Oxidations of Ketones with O2.
TLDR
The role of hppH is uncovered to act not only as a base in the transformation but also as a reductant of the peroxide to the corresponding α-hydroxy ketone, allowing the tuning of reduction efficiency toward higher driving forces, if required.
Oxaziridine-Mediated Catalytic Hydroxylation of Unactivated 3° C−H Bonds Using Hydrogen Peroxide
The design, structural characterization, and evaluation of a unique class of 1,2,3-benzoxathiazine-based oxaziridines as potent O-atom transfer agents for catalytic C−H hydroxylation and alkene
Dioxygen activation under ambient conditions: Cu-catalyzed oxidative amidation-diketonization of terminal alkynes leading to alpha-ketoamides.
  • C. Zhang, N. Jiao
  • Chemistry, Biology
    Journal of the American Chemical Society
  • 2010
TLDR
This chemistry offers a valuable mechanistic insight into this novel Cu catalysis via a radical process where O(2) not only participates as the ideal oxidant but also undergoes dioxygen activation under ambient conditions in this transformation.
Manganese(III)-catalyzed facile direct hydroperoxidation of some heterocyclic 1,3-dicarbonyl compounds.
TLDR
A similar autoxidation of the 5-monosubstituted barbituric acids 5 and 3-butyl-4-hydroxy-2-quinolinone 7 also gave the corresponding hydroperoxides 5 and 8, respectively, in moderate to excellent yields.
Pentanidium-catalyzed enantioselective α-hydroxylation of oxindoles using molecular oxygen.
Pentanidium-catalyzed α-hydroxylation of 3-substituted-2-oxindoles using molecular oxygen has been developed with good yields and enantioselectivities. This reaction does not require an additional
...
...