Generation and Rearrangement of N,O‐Dialkenylhydroxylamines for the Synthesis of 2‐Aminotetrahydrofurans

Abstract

An ew diastereoselective route to 2-aminotetrahydrofurans has been developed from N,O-dialkenylhydroxylamines.T hese intermediates undergo as pontaneous CÀC bond-forming [3,3]-sigmatropic rearrangement followed by aC ÀOb ond-forming cyclization. Ac opper-catalyzed Nalkenylation of an N-Boc-hydroxylamine with alkenyl iodides, and ab ase-promoted addition of the resulting N-hydroxyenamines to an electron-deficient allene,providemodular access to these novel rearrangement precursors.T he scope of this de novo synthesis of simple nucleoside analogues has been explored to reveal trends in diastereoselectivity and reactivity. In addition, ab ase-promoted ring-opening and Mannich reaction has been discovered to covert 2-aminotetrahydrofurans to cyclopentyl b-aminoacid derivatives or cyclopentenones.[*] J. Son, [+] T.

DFT computational insight into Pd(0)-catalyzed oxidative cross-coupling of 1,2-allenyl ketones and aryl boronic acids: Pd(ii)-carbenoid intermediate versus π-allyl-Pd(ii) intermediate

“…[1][2][3][4] Moreover, furan-based functional molecules have potential applications in materials science, especially in the field of furan-based semiconductors for energy conversion and storage. 5 The past decades have witnessed great advancements in furan syntheses using various methods, [6][7][8][9][10] in which the transition-metal-catalyzed cycloisomerization of 1,2-allenyl ketones has attracted remarkable attention [11][12][13][14][15] due to their availability 16,17 (Scheme 1a). The efficient syntheses of furan derivatives via the intramolecular nucleophilic cyclization of 1,2-allenyl ketones were initially reported by Marshall 13 and Hashmi et al 14 (Scheme 1a with G = H, M = Rh I , Ag I , or Pd II ) and subsequently developed by Gevorgyan et al 15 (Scheme 1a with G = alkyl, aryl, halide, silyl, etc., M = Au I , Ag I , Cu I , etc.)…”