tert-Butyl Hypochlorite
tert-Butyl hypochlorite is a versatile and inexpensive oxidizing agent, that allows the conversion of alcohols to ketones, aldehydes to acid chlorides, sulfides to sulfoxides, and hydroxylamines to nitroso compounds. tert-Butyl hypoiodite, which is more reactive, can be prepared from tert-butyl hypochlorite and a metal iodide (M. Ishihara, H. Togo, Synthesis, 2007, 1939. DOI).
Recent Literature
Various alcohols were efficiently converted into the
corresponding nitriles at room temperature by treatment with
tert-butyl hypochlorite, diiodine, or 1,3-diiodo-5,5-dimethylhydantoin (DIH) in the presence of TEMPO, followed by
treatment with diiodine and aqueous ammonia. The nitriles were obtained in good
yields and high purities by a simple extraction of the reaction mixture with
chloroform and subsequent removal of the solvent.
H. Shimojo, K. Moriyama, H. Togo, Synthesis, 2013, 45,
2155-2156.
An efficient, catalytic Hunsdiecker reaction of aliphatic carboxylic acids
affords the corresponding chlorodecarboxylation products in high yields under
mild conditions in the presence of t-butyl hypochlorite and Ag(Phen)2OTf
as catalyst. The reaction exhibits remarkable functional group compatibility.
Z. Wang, L. Zhu, F. Yin, Z. Su, Z. Li, C. Li, J. Am. Chem. Soc., 2012,
134, 4258-4263.
A silver-catalyzed chlorination of benzylic, tertiary, and secondary C(sp3)-H
bonds proceeded with as low as 0.2 mol % catalyst loading at room temperature
under air atmosphere with synthetically useful functional group compatibility.
J. Ozawa, M. Kanai, Org. Lett.,
2017, 19, 1430-1433.
A silver-catalyzed ring-opening chlorination of cycloalkanols enables a
regioselective, efficient, and pratical approach to carbonyl-containing alkyl
chlorides with good yields under mild conditions. The chlorinated products are
readily transformed into other useful synthetic intermediates and drugs.
F.-Q. Huang, J. Xie, J.-Guo Sun, Y.-W. Wang, X. Dong, L-W. Qi, B. Zhang, Org. Lett., 2016, 18,
684-687.
A straightforward, convenient, and efficient oxidative dimerization of aromatic
amines enables an easy access to symmetrical and unsymmetrical azobenzenes under
extremely mild conditions using a unique and cost-effective iodinating reagent.
Y. Takeda, S. Okumura, S. Minakata, Synthesis, 2013, 45,
1029-1033.
An efficient preparation of 2-imidazolines was achieved from aldehydes and
ethylenediamines in the presence of tert-butyl hypochlorite. By this
method, 1,3-bis(imidazolin-2-yl)benzene and 2,6-bis(imidazolin-2-yl)pyridine,
which act as chiral ligands, could be prepared directly from the corresponding
dialdehydes in high yields.
M. Ishihara, H. Togo, Synthesis, 2007,
1939-1942.
The combination of tert-butyl hypochlorite, tetrabutylammonium iodide and
tetrabutylammonium chloride as oxidation system enables the transformation of
ethyl 2-(N-arylcarbamoyl)-2-iminoacetates into the corresponding quinoxalinones
in high yield. Oxygen exhibits a beneficial effect on the reaction.
D. Li, Y. Li, W. Yu, Synthesis, 2017,
49, 4283-4291.
