α-Amination of keto-nitrones via Multihetero-Cope rearrangement employing an imidoyl chloride reagent

α-Aminations of ketone-derived nitrones have been developed via [3,3]-rearrangement of the intermediates generated upon condensation with imidoyl chlorides. Careful reagent selection provides synthetically attractive amino protecting groups. The enediamide or α′-carbamoyl enamide products can be hydrolyzed to the desired carbonyl, or exposed to electrophiles for further α-functionalization

Three-Component Glycolate Michael Reactions of Enolates, Silyl Glyoxylates, and α,β-Enones

Silyl glyoxylates react with enolates and enones to afford either glycolate aldol or Michael adducts. Product identity is controlled by the countercation associated with the enolate. Reformatsky nucleophiles in the presence of additional Zn­(OTf)₂ result in aldol coupling (<b>A</b>), while lithium enolates provide the Michael coupling (<b>B</b>). Deprotonation of the aldol product <b>A</b> with LDA induces equilibration to form the minor diastereomer of Michael product <b>B</b>. This observation suggests that formation of the major diastereomer of Michael product <b>B</b> does not occur via an aldol/retro-aldol/Michael sequence

Mechanically Strong, Flexible Polyimide Aerogels Cross-Linked with Aromatic Triamine

Polyimide gels are produced by cross-linking anhydride capped polyamic acid oligomers with aromatic triamine in solution and chemically imidizing. The gels are then supercritically dried to form nanoporous polyimide aerogels with densities as low as 0.14 g/cm(3) and surface areas as high as 512 m(2)/g. To understand the effect of the polyimide backbone on properties, aerogels from several combinations of diamine and dianhydride, and formulated oligomer chain length are examined. Formulations made from 2,2\u27-dimethylbenzidine as the diamine shrink the least but have among the highest compressive modulus. Formulations made using 4,4\u27-oxydianiline or 2,2\u27dimethylbenzidine can be fabricated into continuous thin films using a roll to roll casting process. The films are flexible enough to be rolled or folded back on themselves and recover completely without cracking or flaking, and have tensile strengths of 4-9 MPa. Finally, the highest onset of decomposition (above 600 °C) of the polyimide aerogels was obtained using p-phenylene diamine as the backbone diamine with either dianhydride studied. All of the aerogels are suitable candidates for high-temperature insulation with glass transition temperatures ranging from 270-340 °C and onsets of decomposition from 460-610 °C

α-Amination of keto-nitrones via Multihetero-Cope rearrangement employing an imidoyl chloride reagent

α-Aminations of ketone-derived nitrones have been developed via [3,3]-rearrangement of the intermediates generated upon condensation with imidoyl chlorides. Careful reagent selection provides synthetically attractive amino protecting groups. The enediamide or α′-carbamoyl enamide products can be hydrolyzed to the desired carbonyl, or exposed to electrophiles for further α-functionalization

Three-Component Glycolate Michael Reactions of Enolates, Silyl Glyoxylates, and α,β-Enones

Silyl glyoxylates react with enolates and enones to afford either glycolate aldol or Michael adducts. Product identity is controlled by the countercation associated with the enolate. Reformatsky nucleophiles in the presence of additional Zn(OTf)(2) result in aldol coupling (A), while lithium enolates provide the Michael coupling (B). Deprotonation of the aldol product A with LDA induces equilibration to form the minor diastereomer of Michael product B. This observation suggests that formation of the major diastereomer of Michael product B does not occur via an aldol/retro-aldol/Michael sequence