Allylstannanes derivatives

Treatment of the title compound with an aqueous base under phase-transfer catalysis conditions generates, by a-elimination, chloro(trifluoromethyl)carbene that can be trapped by cycloaddition to allylsilane and allylstannane derivatives, e.g. formation of 1 and 2. This method represents a fast and mild alternative to the Seyferth method that starts from the same alkyl halide and generates the carbene by thermal decomposition of l-bromo-l,2,2,2-tetra-fluoroethyl(phenyl)mercury (see Section 1.2.1.2.4.1.1). 

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. 

Two approaches for the synthesis of allyl(alkyl)- and allyl(aryl)tin halides are thermolysis of halo(alkyl)tin ethers derived from tertiary homoallylic alcohols, and transmetalation of other allylstannanes. For example, dibutyl(-2-propenyl)tin chloride has been prepared by healing dibutyl(di-2-propenyl)stannane with dibutyltin dichloride42, and by thermolysis of mixtures of 2,3-dimethyl-5-hexen-3-ol or 2-methyl-4-penten-2-ol and tetrabutyl-l,3-dichlorodistannox-ane39. Alternatively dibutyltin dichloride and (dibutyl)(dimethoxy)tin were mixed to provide (dibutyl)(methoxy)tin chloride which was heated with 2,2,3-trimethyl-5-hexen-3-ol40. 

With 2,3-[isopropylidenebis(oxy)]propanal the facial selectivity of the allylstannane generated from tin(II) chloride, the disodium salt of diethyl 2,3-dihydroxybutanoatc, and 3-bromo-1-propene (see preceding section) is overwhelmed by the facial selectivity of the substrate97. Some selectivity was observed in coupling monosaccharide derived allylstannanes with monosaccharide aldehydes99. 

Formation of a vinyl-substituted pyrrolizidine derivative is also observed in case of an allylstan-nane cyclization94. Since the allylstannane moiety is acid sensitive, the iV-acyliminium ion is generated by exposure of the hydroxylactam to methanesulfonyl chloride and triethylamine in dichloromethane. The very rapid cyclization produces the endo-vinyl compound with very high stereoselectivity. 

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... 

Derivatives of trifluoroethanethiol have limited though interesting chemistry. Unfortunately, metallated difluorothioenol chemistry has not been reported, because rapid nucleophilic attack occurs even by hindered bases such as LDA. Nakai et al. exploited this high electrophilicity in a tandem addition/elimina-tion-rearrangement sequence [146], but more recent applications have concerned free radical chemistry (Eq. 46). Chlorination of trifluoroethyl phenyl sulfide followed by exposure to tin hydride in the presence of an allylstannane resulted in C-C bond formation with a reasonable level of stereocontrol [147]. 

Kobayashi and colleagues developed a catalytic enantioselective method for the allylation of imines 24 by substituted allylstannanes 25 with chiral zirconium catalysts 26 and 27 prepared from zirconium alkoxides and l,l -bi-2-naph-thol derivatives (Scheme 10) [19]. The allylation of aromatic imines 24 with 25 afforded the corresponding homoallylic amines 28 in good yields (71-85%) with high stereoselectivities (87-99% ee). 

Stereo specific generation and reactions of allylic alkali and alkaline earth metals have been reviewed121 and solvent-mediated allylation of carbonyl compounds with allylstannanes has been explored.122 Chiral phosphoramides derived from (5 )-proliiie have been used to catalyse asymmetric allylation of aromatic aldehydes by allylic trichlorosilanes.123... 

All the examples described above involved the reaction of diazoacetate derivatives with silver salts to initiate the formation of a putative silver carbene however, other pathways exist. For example, Porcel and Echavarren have reported an intramolecular cyclization of an allylstannane to a pendent alkyne (Scheme 8.22) that involves the intermediacy of a silver carbene.52 As can be seen in Table 8.12, the reactions proceeded in moderate to excellent yield, providing the dienylstannane, while in some cases, reductive destannylation occurred. Several asymmetric reactions were reported with substrate ( )-145d, leading to the formation of the expected adduct in reasonable enantioselectivities (ee = 73-78%) in a preliminary screen with a number of different ligands. 

Dussault and coworkers described the preparation of allylstannanes (116, 117) as part of their synthetic studies (equation 93)731. It is interesting to note the preferred geometries of the products which appear to be dependent on the nature of the stannane employed. In this last example, Yu and Oberdorfer reported the use of free-radical hydrostannylation in their preparation of (tributylstannyl)vinyl-substituted 2-deoxyuridine derivatives (e.g. 118) for use in halogenation and radiohalogenation reactions (equation 94)733. 

In organic syntheses allylsilanes and allylstannanes have been used extensively as allyl anion equivalents during the last two decades [187-190]. The regioselective attack of electrophiles, which finally yields products with allylic inversion (Scheme 43), has been explained by the hyperconju-gative stabilization of carbenium centers by the carbon-silicon or carbon-tin bond in the j3-position [191-196], which has initially been derived from solvolytic experiments [197-199]. 

In contrast to the oxidation of unactivated stannanes, allylic derivatives are expected to be more reactive, and mild conditions and oxidizing agents can be employed successfully. A particularly useful reaction involves the conversion of an allylstannane to die allylic alcdiol, and die commercially available, solid, easily handled m-chloroperbenzoic acid (MCPBA) is die reagent of choice for oxidations employing organic solvents such as dichloromethane. Under these conditions epoxystannanes cannot be isolated and allylic alcohols form direcdy (equation 6). °- ... 

Carbonyl Allylation and Propargylation. Boron complex (8), derived from the bis(tosylamide) compound (3), transmeta-lates allylstannanes to form allylboranes (eq 12). The allylboranes can be combined without isolation with aldehydes at —78°C to afford homoallylic alcohols with high enantioselectivity (eq 13). On the basis of a single reported example, reagent control might be expected to overcome substrate control in additions to aldehydes containing an adjacent asymmetric center. The sulfonamide can be recovered by precipitation with diethyl ether during aqueous workup. Ease of preparation and recovery of the chiral controller makes this method one of the more useful available for allylation reactions. 

In 1995, Porter et al. [34] reported the first excellent results for free radical addition to an electron-deficient alkene by use of chiral zinc complexes. Reaction of the oxa-zolidinone 9 with tert-butyl iodide and allyltributylstannane 30 in the presence of Zn(OTf)2 and a chiral bis(oxazoline) ligand 12 gave the adduct 44 in 92 % yield with 90 % ee (Sch. 18). The chiral bis(oxazoline) complexes derived from ZnCl2 or Mg(OTf)2 gave racemic products. In this reaction, lower allyltin/alkene ratios gave substantially more telomeric products, and a [3 + 2] adduct 45 of the oxazolidinone 9 and the allylstannane 30 was obtained at temperatures above 0 °C. 

The intrinsic difficulty in preparing various titanium derivatives with die desired alkyl group may be overcome by using reagent systems consisting of TiCU as the chelating agent, and a suitable nucleophile like dialkylzinc, allylsilanes, allylstannanes, etc. The utilization of other nucleophiles, like silyl enol ethers will be covert in Part 1 of Volume 2. 

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