Carbometalation carboalumination

All of the reactions discussed above are cyclic carbometallation reactions of metallacycles. Very recently, an interesting Cr-catalyzed carboalumination of propargyl derivatives producing allenes via a carbometallation-elimina-tion sequence has been studied. This reaction provides an asymmetric synthesis of chiral allenes (Scheme 57). 

Syntheses of isolable organometallic species by carbometallations of alkenes are difficult because many side reactions can occur, namely p-hydride elimination and chain propagation. As a consequence, only a few examples have been reported to date, mainly concerning reactions in which the initial carboalumination product is trapped through fast intra-... 

Carbometallation is a term coined for describing chemical processes involving net addition of carbon-metal bonds to carbon-carbon Jt-bonds [1] (Scheme 4.1). It represents a class of insertion reactions. Whereas the term insertion per se does not imply anything chemical, the term carbometallation itself not only explicitly and clearly indicates carbon-metal bond addition but also is readily modifiable to generate many additional, more specific terms such as carboalumination, arylpalladation, and so on. In principle, carbometallation may involve addition of carbon-metal double and triple bonds, that is, carbene- and carbyne-metal bonds, as well as those of metallacycles. Inasmuch as alkene- and alkyne-metal Jt-complexes can also be represented as three-membered metallacycles, their ring expansion reactions via addition to alkenes and alkynes may also be viewed as carbometallation processes (Scheme 4.1). 

Chiral ligands are generally expensive. It is therefore highly desirable to use chiral ligands as catalyst components rather than those of stoichiometric regents. In the desired Zr-catalyzed enantioselective carboalumination of alkenes, for example, chiral ligands should be part of the Zr catalysts. Furthermore, it appears desirable to devise Zr-centened carbometallation processes rather than Al-centered ones. This factor can be potentially serious as both Zr- and Al-centered... 

Negishi, E.-i., Kondakov, D. Y., Choueiry, D., Kasai, K., Takahashi, T. Multiple Mechanistic Pathways for Zirconium-Catalyzed Carboalumination of Alkynes. Requirements for Cyclic Carbometalation Processes Involving C-H Activation. J. Am. Chem. Soc. 1996,118, 9577-9588. 

B.iv.a. p, P -Substituted Alkenybnetals. Carbometallation reactions of 1-alkynes, most notably carboalumination and carbocupration,t collectively provide a powerful route to the synthesis of /3,j8 -substituted alkenylmetals. The alkenylmetals generated in situ may be used directly for Pd- or Ni-catalyzed cross-coupling with aryl electrophiles (Protocol 1). One prototypical example of the carbometallation-cross-coupling tandem process is shown in Scheme... 

Even today, carotenoids and other natural products represented by 1 and/or 2 are synthesized by using the Wittig and related carbonyl oleflnation reactions that are often not highly stereoselective, thus requiring delicate and tedious separations. Carbometallation reactions of alkynes, " ° especially the Zr-catalyzed carboalumination discovered in 1978,[236].[237] jjj conjunction with Pd-catalyzed cross-coupling have provided a totally different carbometallation-cross-coupling tandem protocol for the synthesis of 1 and 2 (Scheme 59). 

Since the preparation of /3,/3-substituted alkenylmetals as the first-generation organometals has been achieved mostly by Zr-catalyzed carboalumination " and carbocupration, the exploitation of Protocol I has largely resorted to these two carbometallation reactions, as indicated by the results summarized in Table 13. Moreover, since it is impractical to carry out methylcupration of alkynes requiring several days at -25 the synthesis of natural products represented by 1 and 2 by the use of Protocol I has mostly been limited to those cases where Zr-catalyzed carboalumination is... 

Normant has reviewed the carbometallation of alkynes to give stereospecific syntheses of alkenyl-metal derivatives, and their addition to aldehydes and ketones to afford allylic alcohols. Specific titanium-catalysed 5yn-hydromag-nesiation of 2-propynylic alcohols (Scheme 16), and the related zirconium-catalysed 5yn-carboalumination of propargylic alcohol itself (also Scheme 16) or its t-butyldimethylsilyl ether (c/. 3, 139 4,160) can both lead to allylic alcohols. 

Other Unsaturated Alcohols. The review mentioned above of carbometallation of alkynes, includes a survey of additions of alkenyl-metal derivatives to epoxides to give homoallylic alcohols. The zirconium-catalysed carboalumination of propargylic systems (Scheme 16) is also applicable to the homopropargylic to homoallylic alcohol transformation. ... 

The carbometalation reaction has been reviewed recently [28-30]. Negishi has demonstrated that zirconium(TV) complexes catalyze the carboalumination of MesAl to various alkynes and enynes [31]. Also the Zr-catalyzed asymmetric carboalumination of aUcenes (ZACA reaction) [32-34] has found important applications in the synthesis of natural products [35-37]. Especially efficient was the asymmetric synthesis of insect pheromones such as (S. / ./ ,S. / ,S)-4,6,8,10,16,18-hexamethyl-docosane (88) (Scheme 8) [38]. 

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