Silanes propargyl

Efforts to tune the reactivity of rhodium catalysts by altering structure, solvent, and other factors have been pursued.49,493 50 Although there is (justifiably) much attention given to catalysts which provide /raor-addition processes, it is probably underappreciated that appropriate rhodium complexes, especially cationic phosphine complexes, can be very good and reliable catalysts for the formation of ( )-/3-silane products from a air-addition process. The possibilities and range of substrate tolerance are demonstrated by the two examples in Scheme 9. A very bulky tertiary propargylic alcohol as well as a simple linear alkyne provide excellent access to the CE)-/3-vinylsilane products.4 a 1 In order to achieve clean air-addition, cationic complexes have provided consistent results, since vinylmetal isomerization becomes less competitive for a cationic intermediate. Thus, halide-free systems with... 

Medium-size cycloalkynes.1 In the presence of BF, etherate, a cobalt com-plexed propargylic ether can undergo an intramolecular alkylation with an allylic silane to provide six-, seven-, and eight-membered complexed cycloalkynes. This reaction is an extension of propargylation of allylsilanes to provide 1,5-enynes (10, 129-130). 

An example of an iron-catalyzed C-C bond formation reaction was reported in 2001 [89]. Treatment of propargyl sulfides 87 with trimethylsilyldiazomethane in the presence of 5 mol% FeCl2(dppb) gave substituted homoallenylsilanes 88 in good to moderate yields (Scheme 3.43). The silanes 88d and 88e, which bear two centers of chirality, were obtained as 1 1 mixtures of diastereomers. Slight diastereoselectivity (2 1) was seen for the formation 88f, which is an axially chiral allene with a sterogenic center. 

Allenyllithium reagents are commonly prepared through lithiation of propargylic halides or by deprotonation of alkynes or certain allenes (Eq. 9.1). Lithiated allenes often serve as precursors to stable allenylmetal compounds such as stannanes or silanes. They can also be employed for the in situ synthesis of allenylzinc, -titanium and -boronate compounds, which can be further transformed to substitution products not accessible from their allenyllithio precursors. 

Lithiation of the allenic stannane in the presence of Me3SiCl gave rise to an 86 14mixture of propargylic and allenic silanes (Eq. 9.7). Sequential lithiation followed by addition of Me3SiCl, on the other hand, afforded the propargylic silane to the near exclusion of the allenic isomer. 

Table 9.28 Synthesis of propargylic silanes by SN2 displacement of propargylic sulfmates.

The route has also been applied to TBS-substituted propargylic mesylates (Eq. 9.39) [45]. Interestingly, the isomeric propargylic silanes are not formed despite the more attractive steric environment for a direct SN2 displacement at the primary center. 

A number of additional methods involve the addition of alkynylsilanes to electrophiles with concomitant 1,3-isomerization to afford allenylsilanes geminally substituted with the electrophile moiety. The first of these methods employed a trimethyl-silyl-substituted propargylic silane as the alkynylsilane and various acetals as the electrophile precursors (Table 9.29) [53], The allenylsilanes are formed without contamination by alkynyl isomers. 

Table 9.29 Synthesis of allenylsilanes from propargylic 1,3-b/s-silanes.

Allenyltrichlorosilanes can also be prepared by Sn2 displacement of propargylic chlorides with a Cu or Ni complex of HSiCl3 [56]. The reaction requires an amine base and a donor solvent such as THF or propionitrile (Table 9.32). Conditions can be adjusted to favor the propargylic or allenic silane, which is not isolated, but treated directly with various aldehydes to afford allenylcarbinols (A) or homopropargylic alcohols (B). These reactions presumably proceed by an SE2 pathway, such that the allenyl products arise from the propargylic silane and vice versa. 

Table 9.33 In situ additions of trichloallenic and/or propargylic silane to aldehydes.

The cross-conjugated trienes have potential in many different types of diversification strategies. For example, the triene clearly lends itself to inter- and intramolecular Diels-Alder reactions. Incorporation of the hydroxymethyl group on the tether allows attachment of functionality suitable for reactions subsequent to the Alder-ene reactions. As depicted in Scheme 8.5, propargyl tosylamides A, alkynyl silanes B, acrylate esters C, and propargyl ethers D can all be readily prepared from 39... 

Scheme 27 Diastereoselective alkylation of propargyl alcohols with silyl enol ethers, allyl silanes and electron-rich arenes...

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