Hydrozirconation multiple reaction

In deciding on the material to be covered in this chapter, limitations had to be set. The first section will present the synthesis of various zirconocene hydrides. The focus of the subsequent sections is to present a general synopsis of the different aspects of the hydrozirconation reactions using 1 not only on carbon-carbon multiple bonds but also on heteropolar multiple bonds. Those aspects of hydrozirconation that were covered in previous reviews [1-5, 27] and in the excellent chapter by Labinger in Comprehensive Organic Synthesis [28] are summarized or briefly mentioned here. For other aspects of organozirconium chemistry not covered by the above-mentioned reviews, the reader is referred to a number of monographs and reviews [29, 30]. 

Note that multiple hydrozirconation reactions can be conducted on the same substrate in a one-pot reaction (Scheme 8-10) [90-93]. 

Despite the great success of the transmetalation process in the enantiose-lective arylation of ketones, its extension to allylation or alkynylation reactions failed, providing the corresponding tertiary alcohols with enantiomeric excesses never higher than 50% ee. On the other hand, more success has been found in the alkenylation of ketones. The process started with the hydrozirconation of terminal alkynes to give the corresponding alkenylzirconium intermediates, which were transmetalated by reaction, in this case, with various ketones in the presence of the HOCSAC ligand. This protocol tolerated the presence of other carbon-carbon multiple bonds on the alkyne, as well as different functionalities and achieved excellent results for alkyl ketones, a,(3-unsaturated ketones and even dialkylketones, as shown in Scheme 4.22. 

The hydrozirconation reaction can lead to a series of reactions formally identical to the hydroboration processes. The addition to multiple carbon—carbon bonds is also a very stereoselective cis) and regioselec-tive (anti-Markownikov type) reaction. Moreover, the isomerization of the addition product towards the formation of the less crowded isomer occurs... 

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