By Payne rearrangement

R,8S)-(+)-Disparlure (12) is the female sex pheromone of the gypsy moth (Lymantria dispar). Advent of Sharpless asymmetric dihydroxylation (AD) allowed several new syntheses of 12 possible. Sharpless synthesized 12 as shown in Scheme 17 [27]. Scheme 18 summarizes Ko s synthesis of 12 employing AD-mix-a [28]. He extended the carbon chain of A by Payne rearrangement followed by alkylation of an alkynide anion with the resulting epoxide to give B. Keinan developed another AD-based synthesis of 12 as shown in Scheme 19 [29]. Mit-sunobu inversion of A to give B was the key step, and the diol C could be purified by recrystallization. 

Scheme 8.9. Reagent-controlled synthesis of L-allose ((+)-AE = Sharpless AE using L-(+)-DIPT (-)-AE = Sharpless AE using d-(-)-DIPT). (a) A Sharpless AE followed by Payne rearrangement and oxidation, (b) Stereodifferentiation of the C-4 and C-5 stereocenters, (c) Chain extension followed by reagent-controlled oxidation of the olefin, (d) Completion of the synthesis.

Stereoselective Inversion of Configuration at More Than One Carbon Atom in Aldonolactones by Payne Rearrangements... 

Sharpless and Masumune have applied the AE reaction on chiral allylic alcohols to prepare all 8 of the L-hexoses. ° AE reaction on allylic alcohol 52 provides the epoxy alcohol 53 in 92% yield and in >95% ee. Base catalyze Payne rearrangement followed by ring opening with phenyl thiolate provides diol 54. Protection of the diol is followed by oxidation of the sulfide to the sulfoxide via m-CPBA, Pummerer rearrangement to give the gm-acetoxy sulfide intermediate and finally reduction using Dibal to yield the desired aldehyde 56. Homer-Emmons olefination followed by reduction sets up the second substrate for the AE reaction. The AE reaction on optically active 57 is reagent... 

The epoxidation of divinyl carbinol constitutes a special case of a dienol epoxida-tion, as the starting diene is not conjugated (Scheme 9.10). Desymmetrization by SAE, followed by a Payne rearrangement, furnishes the vinylepoxide in high yield and with excellent enantioselectivity (compare Table 9.2, Entry 1) [43]. 

In the Payne rearrangement, a 2,3-epoxy alcohol is converted to an isomeric one, by treatment with aqueous base ... 

Aziridines from Amino Epoxides by a Modified Payne Rearrangement... 

A modified Payne rearrangement of amino epoxides catalyzed by Lewis acid or induced by base, represents an interesting but a limited method for the synthesis of fonctionalized aziridines of high enantiopurity. The limitations are primarily due to the accessibility of the starting materials (Scheme 6) [15]. 

An alternative synthesis producing a chiral-substituted 3-azoniaspirooctane, 153 has been published by Liu and co-workers where a modification of the Payne rearrangement was applied to amine epoxide 152 (Equation 35) <1997JCS(P1)511>. 

Scheme 4-20 exemplifies PhS- attack mediated by a Payne rearrangement. The selective ring-opening product can be applied to prepare tetritols.37... 

Payne rearrangement. The Payne rearrangement2 of a primary cts-2,3-epoxy alcohol to a secondary 1,2-epoxy alcohol usually requires a basic aqueous medium, but it can be effected with BuLi in THF, particularly when catalyzed by lithium salts. As a consequence, the rearrangement becomes a useful extension of the Sharpless epoxidation, with both epoxides available for nucleophilic substitutions. Thus the more reactive rearranged epoxide can be trapped in situ by various organometallic nucleophiles. Cuprates of the type RCu(CN)Li are particularly effective for this purpose, and provide syn-diols (3).3... 

Although the Payne rearrangement usually produces mixtures of epoxy alcohols, because the rate of reaction of 2 with any given nucleophile is faster than that of i, the l,2-epoxy-3-alcohols generated in situ can be selectively and irreversibly captured by a nucleophile to afford 3. 

The aza-Payne rearrangement and its use as a synthetically valuable equilibration process has been reviewed. Unusual diazadioxabicyclo[2.2.2]octanes (352) have been obtained by the acid-catalysed rearrangement of A -quinazolinonyl- and A -phthalimido-aziridines derived from 3-phenylcyclohex-2-enol. ° A probable mechanism is outlined in Scheme 108. A-Acyl-2,2-dimethylaziridines have been isomerized by sodium iodide into three isomers whose yields appear to depend... 

Aza-Payne rearrangements, 60, 1 Azaphenanthrenes, synthesis by photocyclization, 30, 1 Azides, synthesis and rearrangement of, 3, 9... 

If a polyol with a primary epoxide is treated with strong base, a rearrangement to the more stable secondary epoxide takes place, as observed by Payne [40]. If an unprotected bromodeoxyaldonolactone is treated with strong base a similar rearrangement may be expected. We found that if 6-bromo-2,6-dideoxy-D-arahzno-hexonolactone (3) (Scheme 5) was treated with 4 molar equivalents of potassium hydroxide, 2-deoxy-L-n bo-hexono-1,4-lactone (15) was isolated as the only product after work up [32]. 

Epoxy-3-alcohols can be derived from 2,3-epoxy-1-alcohols by the base-catalyzed Payne rearrangement as illustrated in step d of Figure 6A.4 [59,64], The rearrangement is completely stereospecific but, because it is reversible, it usually results in an equilibrium mixture of the two epoxy alcohols for which the relative proportions are structure-dependent. Practical synthetic applications of this rearrangement therefore depend on methods that will shift the equilibrium completely in the direction desired. Nucleophiles such as thiolates and amines are... 

While the known desymmetrization of divinylcarbinol by asymmetric Sharpless epoxidation worked well, introduction of the PMB group (which was chosen for its mild removal conditions) required the use of the unstable, non-commercially available PMB bromide (using the commercially available but less reactive PMB chloride, in presence of NaH, led to Payne rearrangement). 

The aza-Payne rearrangement of activated /V-Ts- , -disubsfiluted-aziridinemeth-anols, induced by NaOH in the mixed solvent r-BuOH-H20-THF (4 5 1) or NaH in the mixed solvent THF-HMPA (10 1), and also some iV-Boc-a,a-disubstituted-aziridinemethanols with the latter reagent-solvent combination, provides the corresponding epoxides in up to 99% yield.20... 

Scheme4.83. Payne rearrangement followed by thiol-mediated ring opening of 3-substituted 2,3-epoxy-l-propanols [365],...

Under Payne rearrangement conditions, sodium /-butylthiolate provides 1 -/-butylthio-2,3-diols with very high regioselectivity. The selectivity is affected, however, by many factors including reaction temperature, base concentration, and the rate of addition of the thiol. These sulfides can then be converted to the l,2-epoxy-3-alcohols, which in turn react with a wide variety of nucleophiles specifically at the 1-position (Scheme 9.6). This methodology circumvents the problems associated with the instability of many nucleophiles under Payne conditions.85... 

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