Novel Cycloaddition Reaction of [60]Fullerene with Carbonyl Ylides Generated from Epoxides

Abstract

The thermal reaction of [60]fullerene (C60) with the carbonyl ylides generated in situ from trans-epoxides to give C60-fused tetrahydrofuran derivatives has been investigated. The reaction of C60 with trans-2-benzoyl-3-aryloxiranes afforded only cis-products, while the reaction of C60 with 2-cyano-2-ethoxycarbonyl-3-aryloxiranes gave exclusively or predominantly cis isomers. The isomeric distributions of the latter reactions were drastically affected by the substituent on the phenyl ring.

Anomalous Cis‐Conformation Regioselectivity of Heterocycle‐Fused Sc3N@D3h‐C78 Derivatives

“…[35][36][37] The 1 HNMR spectrum of 3a also shows the extremely similar chemical shifts as that of the cisconformation adduct proposed using the NOESY spectrum ( Figure S11). [35][36][37] Therefore,t he molecular structure of 3a can be confirmed as cis-conformation. Meanwhile,t he 1 HNMR spectrum of 3b has the approximately same chemical shifts as that of the trans-conformation adduct reported by Yang et al, which is consistent with the crystal structure of 3b ( Figure S12).…”

“…The1 ,3-dipolar cycloaddition of C 60 with carbonyl ylides formed via a,b-epoxy ketones is an effective approach for chemical functionalization of fullerenes. [35][36][37] However,t he a,b-epoxy ketones could generate three possible ylide intermediates with two trans-( exo,e ndo) and one cis-( exo,e xo) conformations by the conrotatory of CÀCb ond cleavage, resulting in the uncontrolled formation of both trans-and cisadducts. [38] Considering the considerable discrepancies on the electronic configurations between Sc 3 N@D 3h -C 78 and C 60 ,i n our present work we manage to explore such a1 ,3-dipolar cycloaddition of Sc 3 N@D 3h -C 78 with carbonyl ylide so as to investigate whether Sc 3 N@D 3h -C 78 exhibits the same addition regioselectivity and conformation selectivity as that of C 60 .…”

Theoretical Studies of Reactivity Descriptors, Electronic and Nonlinear Optical Properties of Multifunctionalized Fullerene Ylide With Acetylsalicylic Acid.

“…Prow et al [11] have worked on nano-and micro-particles for skin drug delivery. Zhang et al [12] have experimentally showed the synthesis of C60 fullerene with the end-capped polystyrene, while Wang et al [13] have investigated the novel cycloaddition reaction of fullerene C60 with carbonyl ylides generated from epoxides.…”

α,β-Epoxy Esters in Multiple C–O/C–N Bond-Breaking/Formation with 2-Aminopyridines; Synthesis of Biologically Relevant (Z)-2-Methylene­imidazo[1,2-a]pyridin-3-ones

“…5 Aryl oxiranylcarboxylates/ketones undergo interesting C-C bond heterolysis of the oxirane ring, generating carbonyl ylides 6 that undergo dipolar cycloaddition with various π-systems. For example, the [3+2] cycloaddition of aryl oxiranyl-dicarboxylate/diketone/cyanoketone with indole, 7 alkyne, 8 or [60]fullerene 9 furnishes furo [3,4-b]indole, 2,5-dihydrofuran, or C60-fused tetrahydrofuran, respec-tively. Other significant applications of 2,3-epoxy esters/ketones include [3+2] heterocyclization for the construction of quaternary imidazole skeletons, 10 palladium(0)-catalyzed transformation into β-diketone, 11 and SmI 2 -mediated deoxygenation to produce the α,β-unsaturated ester.…”