Alkenyl zirconocene

Carbon monoxide rapidly inserts into the carbon—zirconium bond of alkyl- and alkenyl-zirconocene chlorides at low temperature with retention of configuration at carbon to give acylzirconocene chlorides 17 (Scheme 3.5). Acylzirconocene chlorides have found utility in synthesis, as described elsewhere in this volume [17]. Lewis acid catalyzed additions to enones, aldehydes, and imines, yielding a-keto allylic alcohols, a-hydroxy ketones, and a-amino ketones, respectively [18], and palladium-catalyzed addition to alkyl/aryl halides and a,[5-ynones [19] are examples. The acyl complex 18 formed by the insertion of carbon monoxide into dialkyl, alkylaryl, or diaryl zirconocenes may rearrange to a r 2-ketone complex 19 either thermally (particularly when R1 = R2 = Ph) or on addition of a Lewis acid [5,20,21]. The rearrangement proceeds through the less stable... 

Access to non-terminal ( ,2)-dienes and ( ,Z, )-trienes 61 is provided analogously through deprotonation of ( , )-4-alkyl-l-chloro-l,3-butadienes followed by insertion of the resultant carbenoid 60 into alkyl- and alkenyl-zirconocene chlorides (Scheme 3.14) [38], The corresponding internal (Z,Z)-dienes and (Z,Z, )-trienes are also readily obtained by insertion of (3-alkynyl carbenoids 62 [44] into alkyl- and alkenylzirconocene chlorides, respectively (Scheme 3.14). Reduction of the triple-bond moiety in the products 63 to afford the cis-alkenes is well known [45—47]. 

Later, it was found that AgAsF6 is even more effective in promoting the addition reactions to aldehydes. Very high yields were obtained with both alkyl- and alkenyl -zirconocenes [51]. The use of AgAsF6 is not only beneficial in terms of reactivity, but is also safer in view of the potential explosive properties of AgC104 [52] (Scheme 8.21). 

More recently, a novel metal-substituted methylenecyclopropene (triafulvene) derivative was obtained when bis(propyne)zirconocene was treated with one equivalent of tris(pentafluorophenyl)borane, followed by excess of benzonitrile (equation 367)430. The first step involves alkynyl ligand coupling to give the isolable Cp2Zr(//-2,4-hexadiyne)B(C6F5)3 betaine. This undergoes a formal intramolecular nitrile insertion into the Zr—C(sp2) c-bond of the adjacent alkenyl zirconocene unit, leading to the zirconium-boron triafulvene-betaine. X-ray analysis of the triafulvene confirmed the planar... 

Unlike the insertion of 2-monosubstituted alkenyl carbenoids (69, 70, and 73), the reaction of 2,2-disubstituted alkenyl carbenoids with alkenyl zirconocene chlorides afforded the expected products as a mixture of stereoisomers. Thus, when 77, derived from the deprotonation of the stereodefined E-l-chloro-2-methyl-l-octene 76, was reacted with -l-hexenylzirconocene chloride 78 at low temperature, a partial inversion of configuration at the alkenyl carbenoid center occurred before or during the rearrangement to afford the expected metalated diene 79 with an E Z isomeric ratio of 58 42 after hydrolysis (see 80, Scheme 27) [53]. The poor stereocontrol was attributed to the metal-assisted ionization [58-60], which promotes the interconversion of the E- to the Z-alkenyl carbenoids 77. The latter occurs at a rate comparable with that of the insertion into organozirconocene chloride, and hence this is responsible for the loss of stereochemistry. 

Terminal alkyne complexes of zirconium, while challenging to isolate, have been implicated in a number of organometallic transformations. Mixing an alkenyl zirconocene 218 with a transient dialkyl zirconocene 111 furnishes a yu-acetylide complex 219 (Scheme 33).112 This reaction is believed to proceed by initial transmetallation to form a zirconocene alkenyl alkyl 220, which undergoes subsequent /3-hydrogen abstraction to generate the terminal alkyne complex 221. This proposed intermediate can be trapped with PMe3 222 from the alkylation of the zirconocene alkenyl bromide with butyllithium. Comparison of the spectroscopic features of this product to the... 

Alkenyl tolyl sulfones. A convenient synthesis involves reaction of alkenyl-zirconocene chlorides (derived from 1-alkynes) with TsCl. 

Acylzirconocene chloride derivatives are readily accessible in a one-pot procedure through the hydrozirconation of alkene or alkyne derivatives with zirconocene chloride hydride and subsequent insertion of carbon monoxide into the alkyl- or alkenyl-zirconocene bond under atmospheric pressure. The pioneering study on the preparation and reactivity of acylzirconocene dated back to the initial study of Schwartz [27] and revealed that an acyl group can be converted into a large variety of carboxylic acid derivatives (Scheme 12.22). 

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