ABSTRACT
Two concise methods for generating oxetan-3-ones from allenes are reported. The first method employs allene epoxidation, opening of the spirodiepoxide by a halide nucleophile, and then intramolecular displacement of a halide by an alkoxide. The second method involves allene epoxidation and then thermal rearrangement of the corresponding spirodiepoxide to oxetan-3-one. The two methods are complementary and stereochemically divergent. Computational analysis of the thermal rearrangement is also described.
Subject(s)
Alkadienes/chemistry , Ethers, Cyclic/chemistry , Spiro Compounds/chemistry , Molecular Structure , StereoisomerismABSTRACT
Allene epoxide formation/opening reaction sequences enabled direct access to diverse products. Described here are a single flask procedure for allene preparation and allene oxidation/derivatization reactions that give, among others, diendiol, diyndiol, α'-hydroxy-γ-enone, dihydrofuranone, butenolide, and δ-lactone products.
Subject(s)
Epoxy Compounds/chemistry , Spiro Compounds/chemistry , Molecular Structure , Oxidation-ReductionABSTRACT
Treatment of omega-epoxynitriles with hydroxylamine affords cyclic aminonitrones in a single step and with high stereoselectivity. The scope of this novel transformation was explored in a series of examples. The aminonitrone products were shown to be useful substrates for further selective elaboration.
