Copper-Catalyzed γ-Cyanation of Aza-Baylis–Hillman Adducts Using Trimethylsilyl Cyanide

Synlett ◽  
2015 ◽  
Vol 26 (08) ◽  
pp. 1026-1030 ◽  
Author(s):  
Lal Yadav ◽  
Arvind Yadav
Keyword(s):  
Nucleophilic Attack ◽  
Tertiary Amines ◽  
Butyl Hydroperoxide ◽  
Trimethylsilyl Cyanide ◽  
Tert Butyl ◽  
Ion Formation ◽  
Tert Butyl Hydroperoxide ◽  
Iminium Ion ◽  
In Situ Formation

A copper-catalyzed γ-cyanation of aza-Baylis–Hillman adducts via iminium ion formation adjacent to benzylic tertiary amines has been developed using tert-butyl hydroperoxide (TBHP) as the external oxidant. The protocol involves in situ formation of 4π-conjugated iminium ion intermediates that undergo nucleophilic attack by cyanide to provide valuable γ-cyanated α,β-unsaturated amines.

Reactions of tert-Butyl Peroxy Esters, XIV. Further Observations on the Preparation of Dialkyl tert-Butylperoxy Phosphates

1975 ◽  
Vol 30 (9-10) ◽  
pp. 732-739 ◽  
Author(s):  
G. Sosnovsky ◽  
E. H. Zaret
Keyword(s):  
Potassium Hydroxide ◽  
Potassium Hydroxide Solution ◽  
Sodium Hydride ◽  
High Yield ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide ◽  
Aqueous Potassium Hydroxide ◽  
Butyl Peroxide

The preparation of dialkyl tert-butylperoxy phosphates (2, R = alkyl) has been achieved by the reaction of the corresponding dialkyl phosphorochloridates (1, R = alkyl) with tert-butyl hydroperoxide either in the presence of pyridine or in the presence of aqueous potassium hydroxide solution. Neither of these routes is suitable for the preparation of dialkyl tert-butylperoxy phosphates in quantity since they yield peroxyphosphates which are contaminated either with the corresponding tetraalkyl pyrophosphates or dialkyl phosphates; the contaminants cannot easily be removed by conventional means from the peroxyphosphates. The method of choice for the preparation in high yield of large quantities of pure dialkyl tert-butylperoxy phosphates involves the interaction of the corresponding dialkyl phosphorochloridate with sodium tert-butyl peroxide which has been prepared in situ from the reaction of tert-butyl hydroperoxide with sodium hydride.

NH4I/tert-Butyl Hydroperoxide-Promoted Oxidative C–N Cleavage of Tertiary Amines Leading to Nitroaromatic Compounds

2017 ◽  
Vol 41 (9) ◽  
pp. 504-508 ◽  
Author(s):  
Ying Shao ◽  
Hao Zheng ◽  
Zhuhong Wu ◽  
Lei Huang ◽  
Jingjing Tong ◽  
...  
Keyword(s):  
Nitroaromatic Compounds ◽  
Tertiary Amines ◽  
One Pot ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide

A NH4I/ tert-butyl hydroperoxide-promoted oxidation of tertiary N-aryl- N,N-dialkylamines in DMSO has been developed to access nitroaromatic compounds. This methodology involves sequential N-dealkylation reactions in one-pot and a radical pathway is proposed.

Cobalt-Catalyzed Oxidative α-Cyanation of Tertiary Aromatic Amines with Trimethylsilyl Cyanide and tert-Butyl Hydroperoxide

Synlett ◽  
2013 ◽  
Vol 24 (10) ◽  
pp. 1283-1285 ◽  
Author(s):  
Norio Sakai ◽  
Akihiro Mutsuro ◽  
Reiko Ikeda ◽  
Takeo Konakahara
Keyword(s):  
Aromatic Amines ◽  
Butyl Hydroperoxide ◽  
Trimethylsilyl Cyanide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide

Oxidative Functionalization of Cyclic N-Arylamines with Nitromethane and TMSCN Using the T-HYDRO/t-BuOK System

Synthesis ◽  
2017 ◽  
Vol 50 (03) ◽  
pp. 617-624 ◽  
Author(s):  
Mariappan Periasamy ◽  
Gunda Rao
Keyword(s):  
Electron Transfer ◽  
Transfer Process ◽  
Electron Transfer Process ◽  
Oxidative Functionalization ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Initial Electron ◽  
Tert Butyl Hydroperoxide ◽  
Iminium Ion

Tertiary cyclic N-arylamines react with nitromethane in the presence of the tert-butyl hydroperoxide (T-HYDRO)/t-BuOK system to give β-nitroamines in up to 90% yield. When TMSCN is used in place of nitromethane, α-aminonitriles are obtained in up to 96% yield. The method is suitable for several unactivated cyclic arylamine substrates. These transformations are rationalized considering the formation of the corresponding iminium ion intermediates via an initial electron transfer process.

scholarly journals α-Acetoxyarone synthesis via iodine-catalyzed and tert-butyl hydroperoxide-mediateded self-intermolecular oxidative coupling of aryl ketones

2017 ◽  
Vol 13 ◽  
pp. 1079-1084 ◽  
Author(s):  
Liquan Tan ◽  
Cui Chen ◽  
Weibing Liu
Keyword(s):  
Oxidative Coupling ◽  
Optimum Conditions ◽  
Butyl Hydroperoxide ◽  
Metal Free ◽  
Tert Butyl ◽  
Radical Intermediates ◽  
Tert Butyl Hydroperoxide ◽  
Aryl Ketones

We present a metal-free method for α-acetoxyarone synthesis by self-intermolecular oxidative coupling of aryl ketones using I2−tert-butyl hydroperoxide (TBHP). Under the optimum conditions, various aryl ketones gave the corresponding products in moderate to excellent yields. A series of control experiments were performed; the results suggest the involvement of radical pathways. Multiple radical intermediates were generated in situ and the overall process involved several different reactions, which proceeded self-sequentially in a single reactor. A labeling experiment using 18O-labeled H2O confirmed that the oxygen in the product was derived from TBHP, not from H2O in the TBHP solvent.

Ni-Catalyzed Oxidative Transamidation of Tertiary Aromatic Amines with N-Acyl Saccharin

Synlett ◽  
2021 ◽  
Author(s):  
Shengzhang Liu ◽  
Lingyun Yang ◽  
Jiasi Tao ◽  
Weijie Yu ◽  
Tao Wang ◽  
...  
Keyword(s):  
Aromatic Amines ◽  
Secondary Amines ◽  
Tertiary Amines ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide

Employment of tertiary amines as the surrogates for secondary amines has prominent superiority in stabilization and easy handle. Herein, a Ni-catalyzed transamidation of N-acyl saccharin amides with tertiary aromatic amines has been reported. By using tert-butyl hydroperoxide (TBHP) as the terminal oxidant, this reaction is featured with a selective cleavage of the C(sp3)–N bonds of the unsymmetrical tertiary aromatic amines depending on the sizes of the alkyl substituents.

Epoxidation of Soybean Oil with Tert-Butyl Hydroperoxide over Manganese (III) Tetraphenylporphyrin Chloride Catalyst

2012 ◽  
Vol 486 ◽  
pp. 328-333
Author(s):  
Ping Ping Jiang ◽  
Wei Jie Zhang ◽  
Ping Bo Zhang
Keyword(s):  
Soybean Oil ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide ◽  
Acid Effect ◽  
Vis Spectroscopy ◽  
Chloride Catalyst ◽  
Optimum Reaction ◽  
High Valent

A new catalytic route was reported for the epoxidation of soybean oil (SBO) with tert-butyl hydroperoxide (TBHP, 65 wt. %) as the clean oxidant over manganese (III) tetraphenylporphyrin chloride (Mn (TPP) Cl) catalyst without carboxylic acid. Effect of tetraphenylporphyrin chloride with various metals (Mn, Fe, Co, Ni and Zn) on SBO epoxidation has been investigated. As biomimetic catalysts, the optimum reaction temperature of the system existed for catalytic activity, which was about 40 °C. The optimum reaction time was 6 h and the suitable promoter was pyrrole considering various factors. The suitable oxidant was TBHP of 65 wt. %. A mechanism for SBO epoxidation was discussed, and a role for high-valent metal peroxide intermediate with double bond directly as part of this mechanism was proposed, which was verified by in situ UV-Vis spectroscopy. The optimized reaction conditions were acquired.

Sign in / Sign up

Export Citation Format

Share Document