5340-64-7

Usage

Synthesis Reference(s)

Tetrahedron Letters, 17, p. 3155, 1976 DOI: 10.1016/S0040-4039(00)93866-8

InChI:InChI=1/C10H20O/c1-5-6-7-8-9(11)10(2,3)4/h5-8H2,1-4H3

Upstream product

• 64-17-5 ethanol 
• 859772-12-6 3-butyl-5,5-dimethyl-hexane-2,4-dione 
• 754-10-9 2,2-dimethylpropionamide 
• 693-25-4 n-pentylmagnesium bromide 
• 23532-74-3 9-butyl-9-borabicyclo<3.3.1>nonane 
• 5469-26-1 1-Bromopinacolon 
• 3282-30-2 pivaloyl chloride 
• 122-56-5 tributyl borane 
• 142-62-1 hexanoic acid 
• 66-25-1 hexanal 
• 75-97-8 3,3-dimethyl-butan-2-one 
• 71-36-3 butan-1-ol 
• 109-67-1 1-penten 
• 630-19-3 pivalaldehyde 

Downstream Products

• 87280-51-1 (4SR,5RS)-4-butyl-2,2-dimethyl-5-phenyl-5-(trimethylsilyl)oxy-3-pentanone 
• 87280-48-6 (4SR,5SR)-4-butyl-2,2-dimethyl-5-phenyl-5-(trimethylsilyl)oxy-3-pentanone 

Relevant academic research and scientific papers

Nitrosotetrazolium-Catalyzed Aerobic Oxidation of Alcohols to the Corresponding Carbonyl Compounds

A mesoionic-nitrosotetrazolium-catalyzed aerobic oxidation of alcohols is reported. In the presence of catalytic amounts of 5-nitroso-1,3-diphenyltetrazolium tetrafluoroborate (5 mol-%) and nitric acid (20 mol-%), a wide range of alcohols are oxidized to the corresponding aldehydes and ketones in yields of 53–100 % at room temperature under ambient air or oxygen conditions. This oxidation shows a strong preference for secondary alcohols over primary alcohols; sterically hindered alcohols are also smoothly oxidized. A mechanism involving a nitroso/NOx catalytic cycle is proposed.

An alkoxyamine compound, alkoxy alcohol oxidation catalyst and method of using the alcohol oxidation

PROBLEM TO BE SOLVED: To provide a novel alkoxyamine compound which can be easily manufactured and applied suitably as an alcohol oxidation catalyst capable of exerting sufficiently high catalytic activity in oxidation of primary and secondary alcohols.SOLUTION: There is provided an alkoxyamine compound with a homoadamantane skeleton represented by the general formula (1) in the figure. [In the formula (1), Rand Rare each independently any one selected from the group consisting of a hydrogen atom and alkyl groups that may be substituted.

Highly efficient aerobic oxidation of alcohols by using less-hindered nitroxyl-radical/copper catalysis: Optimum catalyst combinations and their substrate scope

The oxidation of alcohols into their corresponding carbonyl compounds is one of the most fundamental transformations in organic chemistry. In our recent report, 2-azaadamantane N-oxyl (AZADO)/copper catalysis promoted the highly chemoselective aerobic oxidation of unprotected amino alcohols into amino carbonyl compounds. Herein, we investigated the extension of the promising AZADO/copper-catalyzed aerobic oxidation of alcohols to other types of alcohol. During close optimization of the reaction conditions by using various alcohols, we found that the optimum combination of nitroxyl radical, copper salt, and solution concentration was dependent on the type of substrate. Various alcohols, including highly hindered and heteroatom-rich ones, were efficiently oxidized into their corresponding carbonyl compounds under mild conditions with lower amounts of the catalysts.

Mechanistic insight into aerobic alcohol oxidation using NOx-nitroxide catalysis based on catalyst structure-activity relationships

The mechanism of an NOx-assisted, nitroxide(nitroxyl radical)-catalyzed aerobic oxidation of alcohols was investigated using a set of sterically and electronically modified nitroxides (i.e., TEMPO, AZADO (1), 5-F-AZADO (2), 5,7-DiF-AZADO (3), 5-MeO-AZADO (4), 5,7-DiMeO-AZADO (5), oxa-AZADO (6), TsN-AZADO (7), and DiAZADO (8)). The motivation for the present study stemmed from our previous observation that the introduction of an F atom at a remote position from the nitroxyl radical moiety on the azaadamantane nucleus effectively enhanced the catalytic activity under typical NOx-mediated aerobic-oxidation conditions. The kinetic profiles of the azaadamantane-N-oxyl-[AZADO (1)-, 5-F-AZADO (2)-, and 5,7-DiF-AZADO (3)]-catalyzed aerobic oxidations were closely investigated, revealing that AZADO (1) showed a high initial reaction rate compared to 5-F-AZADO (2) and 5,7-DiF-AZADO (3); however, AZADO-catalyzed oxidation exhibited a marked slowdown, resulting in ～90% conversion, whereas 5-F-AZADO-catalyzed oxidation smoothly reached completion without a marked slowdown. The reasons for the marked slowdown and the role of the fluoro group are discussed. Oxa-AZADO (6), TsN-AZADO (7), and DiAZADO (8) were designed and synthesized to confirm their comparable catalytic efficiency to that of 5-F-AZADO (2), providing supporting evidence for the electronic effect on the catalytic efficiency of the heteroatoms under NOx-assisted aerobic-oxidation conditions.

Copper(I)/ABNO-catalyzed aerobic alcohol oxidation: Alleviating steric and electronic constraints of Cu/TEMPO catalyst systems

Cu/TEMPO catalyst systems promote efficient aerobic oxidation of sterically unhindered primary alcohols and electronically activated substrates, but they show reduced reactivity with aliphatic and secondary alcohols. Here, we report a catalyst system, consisting of (MeObpy)CuI(OTf) and ABNO (MeObpy =4,4′-dimethoxy-2,2′-bipyridine; ABNO = 9-azabicyclo[3.3.1]nonane N-oxyl), that mediates aerobic oxidation of all classes of alcohols, including primary and secondary allylic, benzylic, and aliphatic alcohols with nearly equal efficiency. The catalyst exhibits broad functional group compatibility, and most reactions are complete within 1 h at room temperature using ambient air as the source of oxidant.

Efficient aerobic oxidation of secondary alcohols at ambient temperature with an ABNO/NOx catalyst system

New highly practical methods are presented for aerobic oxidation of secondary alcohols with a nitroxyl radical in combination with HNO3, NaNO2, or both as cocatalysts. Diverse nitroxyls are compared, including several novel bicyclic derivatives. Catalyst systems with the readily available nitroxyls, 9-azabicyclo[3.3.1]nonane-N-oxyl (ABNO) and 9-azabicyclo[3.3.1]nonan-3-one-N-oxyl (keto-ABNO), are optimized in acetic acid or acetonitrile as the solvent. The reactions are compatible with substrates bearing diverse functional groups and proceed efficiently under mild conditions at ambient pressure and temperature.

C-H modification of 2-azaadamantane: Synthesis of C5-functionalized AZADOs for advanced use

Regioselective C-H functionalization of N-protected 2-azaadamantane was achieved via a radical-induced bromination. The obtained 5-bromo-2-azaadamantane is readily transformed to arylated/alkylated 2-azaadamantane N-oxyls [AZADOs], which exhibit high catalytic activities for alcohol oxidation. The Japan Institute of Heterocyclic Chemistry.

3-methyl-4-oxa-5-azahomoadamantane: Alkoxyamine-type organocatalyst for alcohol oxidation

Strong, silent type: A novel alkoxyamine-type organocatalyst has been discovered for alcohol oxidation (see scheme). The alkoxyamine exhibits a high catalytic activity for the oxidation of alcohols to afford the corresponding carbonyl compounds in high yield by oxidative transformation into an oxoammonium ion, which is proposed to serve as an active species. Copyright

METHOD FOR OXIDIZING ALCOHOLS

A method for oxidizing an alcohol, wherein oxidation is performed in the presence of a compound represented by the following formula (I) and a bulk oxidant, which enables efficient oxidation of secondary alcohols as well as primary alcohols, and can attain high reaction efficiency even when air is used as a bulk oxidant.

ALPHA-HYDROGEN SUBSTITUTED NITROXYLS AND DERIVATIVES THEREOF AS CATALYSTS

The present invention relates to novel alpha-hydrogen substituted nitroxyl compounds and their corresponding oxidized (oxoammonium cations) and reduced (hydroxylamine) forms, and to the use of such compounds, inter alia, for (1) oxidation of primary and secondary alcohols to aldehydes and ketones, respectively; (2) resolution of racemic alcohols; (3) desymmetrization of meso-alcohol; (4) as radicals and spin trapping reagents; and (5) as polymerization agents. The present invention further relates to processes for preparing the novel nitroxyl/oxoammonium/ hydroxylamine compounds from the corresponding amines, and to certain novel amine derivatives and their uses. The compounds of the invention as well as the amine precursors are also useful as ligands for transition metals and as organocatalysts in e.g., aldol reactions.