Functionalization of saturated hydrocarbons. Part 4. The Gif system for selective oxidation using molecular oxygen

Barton, Derek H. R.; Boivin, Jean; Gastiger, Michel J.; Morzycki, Jacek W.; Hay-Motherwell, Robyn S.; Motherwell, William B.; Ozbalik, Nubar; Schwartzentruber, Kathy M.

doi:10.1039/p19860000947

Cited by 101 publications

(27 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Thus, the time-honored Gif-systems developed by the late Sir Derek Barton [32] bring about the oxidation of cyclohexane to cyclohexanone while oxidation of cyclohexanol is less ef®cient compared to that of the cycloalkane precursor [33]. While the precise mechanistic details of the Gif-oxidation are not yet entirely clear, some speculation about a rationalization of this conceptually interesting effect are indicated as they may help to exploit other strategies to prevent overoxidation.…”

Section: Thermochemical and Mechanistic Considerationsmentioning

confidence: 97%

Characterization, Orbital Description, and Reactivity Patterns of Transition-Metal Oxo Species in the Gas Phase

Schröder

Schwarz

Shaik

2000

Structure and Bonding

131

View full text Add to dashboard Cite

Metal-oxo and -peroxo species play key roles in catalytic oxidations using transition metals. This contribution addresses gas-phase studies of diatomic metal-oxo species and their properties which turn out to be of prime importance for the understanding of the observed reactivity patterns. A second topic concerns higher transition-metal oxides such as di-and trioxides. For these species there exists a structural dichotomy with the corresponding dioxygen complexes, e.g., MO 2 2 3 M(O 2 ). Most of the metal-based oxidations described involve crossings between surfaces of different spin as crucial steps, and the violation of spin conservation is proposed to determine the reactivity of the late transition-metal oxides. The ability of transition metals to mediate surface crossings via spin-orbit coupling is introduced as a key aspect in oxidation catalysis which has as yet not been fully appreciated. It is further outlined how these fundamental properties may relate to the properties of metal-oxo catalysts in the condensed phase.

show abstract

Section: Thermochemical and Mechanistic Considerationsmentioning

confidence: 97%

Characterization, Orbital Description, and Reactivity Patterns of Transition-Metal Oxo Species in the Gas Phase

Schröder

Schwarz

Shaik

2000

Structure and Bonding

131

View full text Add to dashboard Cite

show abstract

“…[J41 In these approaches oxygen transfer to the olefin is effected by chiral manganese(n1) complexes with chiral salen h g a n d~, [~~] and iodosylbenene or hypochlorite,li""-1441 hydrogen peroxide,[' 5"1 and even molecular oxygen/ aldehydes is used. ['* '1 As a typical example, the epoxidation of 164 with NaOCl in the presence of catalyst 166 gave 165 with 98 We wish to discuss another aspect of the cytochromeP-450 type oxidation of alkenes, namely. the catalytic oxidative transformation of alkenes into cc-ketols.…”

Section: Metal-catitlyled Oxidationsmentioning

confidence: 99%

Synthetic Aspects of Metal‐Catalyzed Oxidations of Amines and Related Reactions

Murahashi

1995

Angew. Chem. Int. Ed. Engl.

523

224

View full text Add to dashboard Cite

The metabolism of amines is governed by a variety of enzymes such as amine oxidase, flavoenzyme, and cytochrome P‐450. A wide variety of compounds are produced such as ammonia and alkaloids in selective and clean oxidation reactions that proceed under mild reaction conditions. Simulation of the functions of these enzymes with simple transition metal complex catalysts may lead to the discovery of biomimetic, catalytic oxidations of amines and related compounds. Indeed, metal complex catalyzed oxidations have been found to proceed with high efficiency. The first section of this review discusses the dehydrogenative oxidations of amines with transition metal catalysts by transition metal catalysts that simulate amine oxidase. The second section highlights the catalytic oxidation of secondary amines to nitrones by simulation of flavoenzymes. The third section describes the simulation of the function of cytochrome P‐450 with lowvalent ruthenium complexes and peroxides. Biomimetic ruthenium‐catalyzed oxidations of tertiary amines, secondary amines, and other substrates such as amides, β‐lactams, nitriles, alcohols, alkenes, ketones, and even nonactivated hydrocarbons can be performed selectively under mild conditions. These three general approaches provide highly useful strategies for synthesis of fine chemicals and biologically active compounds such as alkaloids, amino acids, and β‐lactams.

show abstract

“…[5,6] Remarkably, there were no rotamers from the BOC protecting group present in the spectra of substances 9-11 and 15-18, possibly due to conformational rigidisation by hydrogen bonds between the hydroxy groups and the nitrogen atom. Bromination of the a-hydroxyketone 9 results in a bromo derivative, [21] which is transformed into the cyclohexenone 10 by dehydrobromination with DBU. [22] Attempts to introduce an additional CÀC double bond by allylic bromination, [23] by introduction of a phenylselenyl substituent in the allyl position [24] followed by oxidation of 11 (Scheme 3) or by direct oxidation of 10 with DDQ, [25] however, were unsuccessful.…”

Section: Chemistry-synthesis Of the Scyphostatin Analoguementioning

confidence: 99%

Synthesis and Antiapoptotic Activity of a Novel Analogue of the Neutral Sphingomyelinase Inhibitor Scyphostatin

et al. 2005

View full text Add to dashboard Cite

The enantioselective synthesis of an analogue of scyphostatin, a potent inhibitor of the neutral sphingomyelinase, is described. The synthesis starts with cyclohexanone and a protected D-serine derivative. The key step is an asymmetric hydroxylation to access a hydroxycyclohexanone, which is transformed into a substituted hydroxycyclohexenone. This is converted into the scyphostatin analogue 14, a chemically and metabolically stabilised compound lacking the epoxy function of the natural congener and carrying a palmitic acid group instead of the native trienoyl residue. An evaluation of the biological activity of 14 revealed neutral sphingomyelinase inhibition in several in vivo test systems (monocytes, macrophages, hepatocytes) monitoring antiapoptotic effects and the inversion of phorbolester-induced translocation of green fluorescent protein labelled kinase (protein kinase C-alpha).

show abstract

Functionalization of saturated hydrocarbons. Part 4. The Gif system for selective oxidation using molecular oxygen

Cited by 101 publications

References 2 publications

Characterization, Orbital Description, and Reactivity Patterns of Transition-Metal Oxo Species in the Gas Phase

Characterization, Orbital Description, and Reactivity Patterns of Transition-Metal Oxo Species in the Gas Phase

Synthetic Aspects of Metal‐Catalyzed Oxidations of Amines and Related Reactions

Synthesis and Antiapoptotic Activity of a Novel Analogue of the Neutral Sphingomyelinase Inhibitor Scyphostatin

Contact Info

Product

Resources

About