Addition allylstannanes

The a-bromo-7-lactone 901 undergoes smooth coupling with the acetonyltin reagent 902 to afford the o-acetonyl-7-butyrolactone 903[763j. The o-chloro ether 904, which has no possibility of //-elimination after oxidative addition, reacts with vinylstannane to give the allyl ether 905, The o -bromo ether 906 is also used for the intramolecular alkyne insertion and transmetallation with allylstannane to give 907[764],... 

Lewis acid catalyzed carbonyl addition of allylsilanes (Section D.l.3.3.3.5.) and allylstannanes (Section D.l.3.3.3.6.) usually proceed with clean allylic inversion (Section D.l.3.3.1.2.). Since these compounds are prepared by several routes and are also stable enough to be purified, each regioisomer can be approached. 

Since the double-bond configuration is established in the final elimination step from a /t-silicon-(or tin-) substituted carbenium ion in a conformation of lowest energy, often high E selectivity is observed. In reactions of allylstannanes, catalyzed by tin(TV) chloride or titanium(IV) chloride, occasionally a metal exchange occurs, followed by the pericyclic addition pathway leading to the iwti-diastereomers17 19. A more detailed discussion is given in Section D.1.3.3.3.5. 

Finally, the in situ formation and thermolysis of trialkyltin ethers derived from tertiary homoal-lylic alcohols has been developed into a useful allylstannane synthesis39,40. This fragmentation is the reverse of the addition of an allylstannane to a ketone41. 

Allyltrialkoxy- or -tris(dialkylamino)titanium reagents are not capable of chelation-controlled addition reactions with oxy- or amino-substituted carbonyl compounds due to their low Lewis acidity87. To attain chelation control, the application of allylsilanes (Section 1.3.3.3.5.2.2.) and allylstannanes (Section I.3.3.3.6.I.3.2.) in the presence of bidentate Lewis acids like titanium(IV) chloride, tin(lV) chloride or magnesium bromide are the better options. 

The diastereoselectivity is lower in the additions of allylstannanes and allyl Grignards. 

AUylzirconium complexes are conveniently obtained by the regio- and stereoselective hydrozirconation of allene [127-133] and can be, for example, used subsequently for the MAO-catalyzed allylzirconation of alkynes to prepare enyne derivatives [132]. Alternatively, the preparation of (E)-l,3-dienes from aldehydes and the appropriate allylstannane zirconocene derivative (R = SnBu,) is accomplished (Scheme 8-17) [131], Note that addition of [Cp2Zr(H)Cl[n (1) on the aUenyl reagent with the... 

The majority of catalytic enantioselective allylation reactions involve the chiral Lewis-acid-catalysed additions of allylsilanes or allylstannanes to carbonyl compounds. Monothiobinaphthol has been used by Woodward et al. as a chiral promoter in the enantioselective catalytic allylation of aryl ketones with impure Sn(allyl)4, prepared from allyl chloride, air-oxidised magnesium and SnCl4. Therefore, the allylation of arylketones in these conditions was achieved very efficiently, since the corresponding allylic alcohols were formed in... 

Use of di-( -butyl)stannyl dichloride along with an acyl or silyl halide leads to addition of allylstannanes to the aldehydes.1728,172 Reaction is also promoted by butylstannyl trichloride.173 Both SnCl4 and SnCl2 also catalyze this kind of addition. 

Allylstannane additions to aldehydes can be made enantioselective by use of chiral catalysts. A catalyst prepared from the chiral binaphthols R- or S-BINOL and Ti(0-i-Pr)4 achieves 85-95% enantioselectivity.187... 

The key step in the synthesis of A-ring fragment 50 [56] is the chelation-controlled addition of allylstannane 53 to aldehyde 52, which sets the C7 stereocenter and introduces the C8 gem-dimethyl moiety. Aldehyde 52 is itself prepared from 1,3-propanediol using the author s protocol for titanium-catalyzed enantioselective allylstannation [57], which sets the C5 stereocenter, followed by chelation-controlled Mukaiyama aldol addition [58] to establish the C3 stereocenter (Scheme 5.6). 

Conversion of the A-ring aldehyde 50 to hydroxyallylsilane 57 is accomplished in a three-step sequence involving addition of allylstannane 49 followed by oxidation-reduction for diastereomeric enrichment at Cll. With both hydroxyallylsilane 57 and aldehyde 51 in hand, intermolecular Prins pyran annulation proceeds smoothly to furnish the tricyclic compound 58 in 61 % isolated yield. 

Allylstannanes undergo diasterospecific additions to chiral a-alkoxyaldehydes, as shown in reaction 45295. Stereospecific additions to aldehydes are attained in the presence of... 

A case of the addition of an allylstannane to aldehydes has been reported by Tagliavini to proceed with appreciable enantioselectivity (Scheme 6.15) [40]. A notable feature of the Zr-catalyzed transformations is that they proceed more rapidly than the corresponding Ti-catalyzed processes reported by the same research team (see Scheme 6.16). Furthermore, C—C bond formation is significantly more efficient when the reactions are carried out in the presence of 4 A molecular sieves the mechanistic rationale for this effect is not known. It should be noted that alkylations involving aliphatic aldehydes are relatively low-yielding, presumably as the result of competitive hydride transfer and formation of the reduced primary alcohol. 

Scheme 6.15. Zr-catalyzed enantioselective addition of allylstannanes to aldehydes is more facile than the corresponding Ti-catalyzed processes.

For the purpose of carrying out carbonyl addition reactions, allylstannanes can be prepared in situ from metallic tin and an allyl halide (Barbier conditions),259 for example, Equation (93).260... 

Similar reactions can be carried out by using a tin(ll) compound rather than metallic tin.264-266 The allylstannanes are still easily handled but are much more reactive than the simple alkylstannanes, and their principal modes of reaction are summarized in Scheme 8. All these reactions, and particularly the carbonyl addition reactions (X=Y = R2C=0), are important in organic synthesis, and are covered in that respect in Volume 9. Only... 

Allylstannanes are unreactive toward weakly electrophilic enones such as cyclohexenone, but enone additions have been established with the more electrophilic 2-ethoxycarbonylallylstannane (Equation (108)).290... 

Most of the current interest, however, is directed toward the use in synthesis of the formation of a carbon-carbon bond by the addition of an allylstannane to carbonyl groups (Equation (114)). These reactions have been thoroughly reviewed,16 18 19 299-301 and are covered in Section 9.08.3 of this series, and will not be considered in detail here. 

The catalytic activity of the trityl moiety was unobjectionably adjusted in the addition reaction of the allylstannanes to aldehydes [148]. In this allylation process the trityl chloride 52, due to its disposition to partially ionic character of the halogen bonding, was employed as a catalyst in the complementary tandem with weak Lewis acid TMSCl (Scheme 57). The excess of the silyl component was necessary in order to release the trityl catalyst from the intermediate to complete the catalytic cycle. The achieved yield was 93%, when trityl chloride 52 was used. 

Although these allylic stannanes are rather resistant to uncatalysed or Lewis acid-catalysed carbonyl addition , they are valuable, shelf-stable homoenolate reagents (see Section IV.C.5), which are activated by Lewis acids or lithiodestannylation. Titanium tetrachloride converts the allylstannanes stereospecifically with inversion into very reactive intermediates (equation 83) . Both isomers, (R,Z)- and (5, )-315, are transformed... 

Another class of compounds which undergo addition reactions with alkyl radicals are allylstannanes. The chain is propagated by elimination of the trialkylstannyl radical.229 230 231... 

The radical source must have some functional group X that can be abstracted by trialkylstannyl radicals. In addition to halides, both thiono esters and selenides are reactive. Allyl tris(trimethylsilyl)silane can also react similarly.232 Scheme 10.11 illustrates allylation by reaction of radical intermediates with allylstannanes. 

SCHEME 26. Eavored antHs. lJ addition of singlet oxygen to allylstannanes... 

In addition to allylsilanes, CM can also be applied to allylstannanes, which serve as valuable reagents for nucleophilic additions and radical reactions.To date, only eatalyst 1 has been shown to demonstrate CM reactivity in the preparation of 1,2-disubstituted allylstannanes, as ruthenium catalysts were found to be inactive in the presence of this substrate class.Poor stereoselectivities were generally observed, with the exeeption of one instance of >20 1 Z-selectivity in the reaction of allyltributylstannane with an acetyl-protected allyl gluco-side. 

Alkyl halides possessing / -hydrogens are usually poor substrates for carbonylative cross-coupling due to competitive / -hydride elimination/ Allyl chlorides can be used in carbonylative cross-coupling with allylstannanes/ phenyl-, 3-furyl, or vinylstannanes " to afford allylketones in modest to good yields. Divinylketones can be accessed through the reaction of vinylstannanes with vinyl iodides or vinyl triflates, with the latter requiring the addition of LiCl. Synthetic potential of this method has been proved in the formation of macrocyclic ketone jatrophone. In the reaction of vinyl triflates with tetramethyltin or aryltrimethylstannanes the additional activation by ZnCle is required. 

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