The peroxide transfer reaction

Abstract

A new method for synthesis of dialkyl peroxides is described which is based on the novel peroxide transfer reaction between germanium or tin peroxides and alkyl trifluoromethanesulfonates (triflates). Yields are generally superior to those obtainable by alkylation of hydrogen peroxide with alkyl methanesulfonates (mesylates) in the presence of base, especially for secondary alkyl peroxides. Mixed dialkyl peroxides are obtained from the reaction of tri-M-butyltin peralkoxide with alkyl triflates. Bis(tri-n-butyltin) peroxide reacts with alkyl triflates to afford symmetrical dialkyl peroxides, and with alkyl bistriflates to afford fiveto eight-membered cyclic peroxides. The strained bicyclic peroxide nucleus of prostaglandin endoperoxides, 2,3-dioxabicyclo[2.2.1]heptane, is obtained in 22% yield from the bistriflate of m-l,3-cyclopentanediol.

Stereocontrolled Formation of Epoxy Peroxide FunctionalityAppended to a Lactam Ring

“…The above results are markedly different from epoxidations of the carbocyclic analogues in the presence of TBHP−VO(acac) 2 , and suggest substantially different mechanisms. Tin(IV) alkyl peroxides are known to displace trifluoromethanesulfonates to give dialkyl peroxides, and cyclic peroxides can be prepared from bis(trifluoromethanesulfonates) and bis(tri- n -butyltin)peroxide . This well-established use of tin(IV) in the context of peroxides as nucleophiles is consistent with the catalytic formation of the α-peroxy lactams, which in turn strongly suggests an acyliminium intermediate, presumably 9 (Scheme ), that could be subject to both α- and β-addition of nucleophiles (here peroxide).…”

Ene reactions of allylic tin compounds with singlet oxygen and with 4-phenyl-1,2,4-triazoline-3,5-dione

“…6, 0.87 (9 H, t, J 7.30), 1.16 (6 H, t, J 8.39), 1.30 (6 H, m), 1. 47 33 and 41 all decomposed on silica gel as discussed in the text; their NMR characteristics are given in Table 2.…”

Synthesis and Biological Studies on Dinuclear Gold(I) Complexes with Di-(N-Heterocyclic Carbene) Ligands Functionalized with Carbohydrates

“…All commercially available reagents (Sigma-Aldrich, Darmstadt, Germany) were used as received without additional purification steps. The reagents a [ 32 ], b [ 52 ], 1,3-propylenebistriflate [ 53 ], and complex 6 [ 36 ] were prepared according to literature procedures. The NMR spectra were recorded on a Bruker Avance 300 (Bruker, Billerica, MA, USA; 300.1 MHz for 1 H and 75.5 MHz for 13 C) at 298 K unless otherwise stated; chemical shifts (δ) are reported in units of ppm relative to the residual solvent signals.…”