Allylic alcohols synthesis from

AUyl transfer reactions, 73, 1 Allylic alcohols, synthesis from epoxides, 29, 3 by Wittig rearrangement, 46, 2 Allylic and benzylic carbanions, heteroatom-substituted, 27, 1 Allylic hydroperoxides, in... 

In the first of these sequences, often called the Torgov-Smith synthesis, the initial step consists in condensation of a 2-alkyl-cyclopentane-l,3-dione with the allyl alcohol obtained from 6-methoxy-l-tetralone and vinylmagnesium chloride. Although this reaction at first sight resembles a classic SN displacement, the reaction is actually carried out with only a trace of base. 

Koncienski295 reported a new synthesis of allylic alcohols starting from the allylic sulfones via formation of epoxysulfones. 

Dehydrobromination of bromotrifluoropropene affords the more expensive trifluoropropyne [237], which was metallated in situ and trapped with an aldehyde in the TIT group s [238]synthesis of 2,6-dideoxy-6,6,6-trifluorosugars (Eq. 77). Allylic alcohols derived from adducts of this type have been transformed into trifluoromethyl lactones via [3,3] -Claisen rearrangements and subsequent iodolactonisation [239]. Relatively weak bases such as hydroxide anion can be used to perform the dehydrobromination and when the alkyne is generated in the presence of nucleophilic species, addition usually follows. Trifluoromethyl enol ethers were prepared (stereoselectively) in this way (Eq. 78) the key intermediate is presumably a transient vinyl carbanion which protonates before defluorination can occur [240]. Palladium(II)-catalysed alkenylation or aryla-tion then proceeds [241]. 

Compatibility of asymmetric epoxidation with acetals, ketals, ethers, and esters has led to extensive use of allylic alcohols containing these groups in the synthesis of polyoxygenated natural products. One such synthetic approach is illustrated by the asymmetric epoxidation of 15, an allylic alcohol derived from (S)-glyceraldehyde acetonide [59,62]. In the epoxy alcohol (16) obtained from 15, each carbon of the five-carbon chain is oxygenated, and all stereochemistry has been controlled. The structural relationship of 16 to the pentoses is evident, and methods leading to these carbohydrates have been described [59,62a]. 

Certain chiral epoxides can be prepared from fl-hydroxyselenides (e.g., 43), typically intermediates for allylic alcohol synthesis. The novel reactivity of these substrates seems to be restricted to those cyclic compounds in which the hydroxy and the selenoxide groups can achieve an antiperiplanar disposition [95TL5079],... 

However, the regioselectivity is also affected by statistical factors and if these two effects are in opposition, then the regioselectivity may not be very great, e.g. Scheme 22. However, one extremely useful aspect of the regioselectivity of selenoxide elimination is the marked preference for elimination to take place away from an electronegative atom. P-Oxygen substituents in particular are very effective at directing the elimination away from themselves, as indicated in equations (41) and (42), and this forms the basis of a very useful allylic alcohol synthesis (Section 5.3.4.2.2). ... 

The stereoselectivity seen in the reduction of the seven-membered ketone above has proved to be general. This particular result, rationalized by the propensity for pseudoaxial hydride addition under Luche conditions, proved useful in the convergent total synthesis of Gymnocin-A, a polycyclic ether toxin isolated from the red tide dinoflagellate—Karenia mikimotoi.u The Luche reduction was used for the production of allylic alcohol 9 from ketone 8 in 84% yield. Luche conditions were similarly applied to the synthesis of the related polycyclic ether toxin gambierol.12... 

The synthesis of enantioenriched acyl chloride 54 was originally conducted using a modification of procedures described by Villieras and coworkers for the preparation of racemic alcohol 55 (Scheme 12). Thus, the synthesis commenced with the preparation of racemic allylic alcohol 55 from 2,5-dimethoxytetrahydrofuran. The alcohol was resolved enzymatically, following procedures reported by Ogasawara, to provide enantioenriched alcohol (S)-55 in 50% yield and 99% ee. Protection of the alcohol with the sterically encumbered ferf-butyl dimethylsilyl group allowed a diastereoselective copper(I)-mediated conjugate addition of methyl magnesium bromide to... 

The required stereochemical implements are all present in the allylic alcohol (132) from which (133) is derived. The C-8 and C-9 chiral centres of P G p2 are the only ones not represented in (133) but the instruments for their stereocontrolled creation are present as will become apparent. The ester (133) can therefore be regarded as the chiral lynch-pin for the synthesis. 

At first, as shown in Scheme 5, we pursued the synthesis of intermediate 28, a substrate for the key [2,3]-Wittig rearrangement, starting from known enan-tiomerically pure 14 [17]. The route to allyl alcohol 13 from 14 has been established (30% overall yield in 11 steps) in Danishefsky s total synthesis of ( )-2 (cf. Section Total Synthesis of ( )-Sesquicillin [Zhang and Danishefsky] ) [13]. Therefore, we decided to follow the Danishefsky s route with some improvements of the reaction steps and conditions (cf. 29—>30—>18, 19- [31] 20), which allowed an increase in the total... 

The sex attractant of the female winter moth has been identified as the tetraene CH3(CH2)8CH=CHCH2CH=CHCH2CH=CHCH=CH2 Devise a synthesis of this material from 3 6 hexadecadien 1 ol and allyl alcohol... 

The remarkable stereospecificity of TBHP-transition metal epoxidations of allylic alcohols has been exploited by Sharpless group for the synthesis of chiral oxiranes from prochiral allylic alcohols (Scheme 76) (81JA464) and for diastereoselective oxirane synthesis from chiral allylic alcohols (Scheme 77) (81JA6237). It has been suggested that this latter reaction may enable the preparation of chiral compounds of complete enantiomeric purity cf. Scheme 78) ... 

A salient structural feature of intermediate 18 (Scheme 2b), the retrosynthetic precursor of aldehyde 13, is its y,r5-unsaturated ester moiety. As it turns out, the Johnson ortho ester variant of the Clai-sen rearrangement is an excellent method for the synthesis of y,<5-unsaturated esters.11 In fact, the Claisen rearrangement, its many variants included, is particularly valuable in organic synthesis as a method for the stereocontrolled construction of trans di- and tri-substituted carbon-carbon double bonds.12,13 Thus, it is conceivable that intermediate 18 could be fashioned in one step from allylic alcohol 20 through a Johnson ortho ester Claisen rearrangement. In... 

Johnson s classic synthesis of progesterone (1) commences with the reaction of 2-methacrolein (22) with the Grignard reagent derived from l-bromo-3-pentyne to give ally lie alcohol 20 (see Scheme 3a). It is inconsequential that 20 is produced in racemic form because treatment of 20 with triethyl orthoacetate and a catalytic amount of propionic acid at 138 °C furnishes 18 in an overall yield of 55 % through a process that sacrifices the stereogenic center created in the carbonyl addition reaction. In the presence of propionic acid, allylic alcohol 20 and triethyl orthoacetate combine to give... 

The most crucial stage in the synthesis has been reached. The goal of constructing the L-hexoses from allylic alcohols 36 and 44 can be achieved only in the event that the two diastereotopic olefin... 

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