A homo [3+2] dipolar cycloaddition: the reaction of nitrones with cyclopropanes.
نویسندگان
چکیده
Cycloadditions are among the most trusted of chemical transformations available to the synthetic chemist. The predictability of the transition state based on steric and electronic considerations allows for the strategic construction of complex molecular assemblies. While the Diels–Alder reaction has received the most attention, 1,3-dipolar cycloadditions have also maintained a place of prominence in the toolbox of the synthetic chemist. During recent studies of the synthetic reactions of cyclopropanediesters, we were struck by the fact that simple 1,1cyclopropane diesters behaved very much like a,b-unsaturated carbonyl compounds in their ability to react with nucleophiles in what could be considered a homo-Michael addition (an observation not unnoticed by others). The strained bonds in the cyclopropane ring have long been considered to have a significant p character and in 1,1cyclopropane diesters this bond can be polarized and further weakened by coordination of a Lewis acid to one or both of the ester moieties. This reactivity suggests that such compounds are one-carbon homologues of electron-deficient olefins, and led us to investigate their reactions with nitrones in what is naively a dipolar homo [3+ 2] cycloaddition (Scheme 1) resulting in the formation of tetrahydro-1,2oxazines. In this communication we disclose the first reaction of a nitrone with a cyclopropane to produce a
منابع مشابه
Yb(NTf2)3-catalyzed [3 + 3] cycloaddition between isatin ketonitrones and cyclopropanes to construct novel spiro[tetrahydro-1,2-oxazine]oxindoles.
Yb(NTf(2))(3)-catalyzed [3 + 3] cycloaddition between isatin ketonitrones and cyclopropanes is described. A variety of spiro[tetrahydro-1,2-oxazine]oxindoles were obtained in moderate to good yields along with good regioselectivities. This is the first example of the intermolecular [3 + 3] cycloaddition between ketone-derived nitrones and cyclopropanes.
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ورودعنوان ژورنال:
- Angewandte Chemie
دوره 42 26 شماره
صفحات -
تاریخ انتشار 2003