[695-64-7]  · C6H10ClNO  · 1-Chloro-1-nitrosocyclohexane  · (MW 147.5)

(electrophilic [NH2+] for alkenes and can function as a dienophile for [4 + 2] reactions)

Physical Data: bp 52 °C/12 mmHg.

Solubility: sol in wide range of organic solvents.

Form Supplied in: solid; widely available.

Preparative Methods: the most commonly used method is the reaction of cyclohexanone oxime with a chlorinating agent such as t-Butyl Hypochlorite in trichlorofluoromethane (eq 1).1

1-Chloro-1-nitrosocyclohexane shows a wide range of reactivity towards different functional groups. Deboer first demonstrated the reactivity of this reagent by reacting it with allylic alkenes such as phenylpropene to give cyclohexylidene-N-(2-phenyl)-prop-1-en-3-yl nitrone hydrochloride in 76% yield (eq 2).2

Other authors have shown that this reagent can be used effectively in the synthesis of polyhydroxylated cyclohexyl derivatives, alkaloids, and amino acids. 1-Chloro-1-nitrosocyclohexane reacts with 1,3-butadiene in ethanol to give 3,6-dihydro-1,2-dioxine (eq 3).3 Kresze in 1981 reported a synthesis of polyhydroxy amino compounds by utilizing the reactivity of 1-chloro-1-nitroso compounds towards dienes such as trans-1,3-cyclohexadien-5,6-diyl diacetate (eq 4).4 In 1984, Kibayashi reported a facile route to naturally occurring tropane alkaloids.5 The approach employs a Diels-Alder cycloaddition of cyclohepta-1,3-dienes with nitroso compounds followed by an intramolecular C-N bond formation (eq 5).

Recently, Oppolzer demonstrated the use of 1-chloro-1-nitrosocyclohexane as a convenient electrophilic nitrogen source in the asymmetric synthesis of amino acids and a-hydroxyamino acids.6 Treatment of an N-alkylsultam with Sodium Hexamethyldisilazide followed by 1-chloro-1-nitrosocyclohexane gave diastereomerically pure crystalline N-hydroxy amino acids (eqs 6 and 7).

1. Luttke, W.; Diekman, H. AG(E) 1968, 7, 387.
2. Schenk, C.; DeBoer, T. J. TL 1979, 35, 147.
3. Lindfors, K. R.; Labuziewicz, H. H 1989, 29, 929.
4. Kresze, G.; Dittel, W. LA 1981, 610.
5. Kibayashi, C.; Watanbe, Y.; Iida, H. TL 1984, 25, 5091.
6. (a) Oppolzer, W.; Tamura, O.; Deerberg, J. HCA 1992, 75, 1965. (b) Oppolzer, W.; Tamura, O. TL 1990, 31, 991.

Gary E. Keck & Anandan Palani

University of Utah, Salt Lake City, UT, USA

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