Addition reactions functionalized Grignard reagents

Initial studies on the application of these catalysts to allylic substitution reactions showed that the arenethiolate moiety functions as an excellent nontransferable group, and that the regioselectivity can be completely reversed by suitable changes in the reaction parameters [33]. If the reaction between geranyl acetate and n-BuM gl was carried out inTHFat—30°C with fast addition of the Grignard reagent to the reaction mixture, complete a selectivity was obtained. Raising the tempera-... 

Also other reaction types have been dealt with in CHEC(1984) and CHEC-II(19%) like reduction to alcohols (e.g., sodium borohydride), Wolff Kishner reduction, nucleophilic addition via reaction with Grignard reagents or organo-lithium compounds, and formation of imine type functional groups (e.g., hydrazones). New examples are the reaction of... 

Ab initio calculations also confirm that the use of an allyl magnesium alkoxide in place of the alcohol functionality will lead to high or complete stereoselectivity (138). When homoallylic alcohols are used, the Kanemasa protocol afforded the respective isoxazolines with poor stereoselectivity ( 55 45) in the case of terminal aUcenes, but with very high diastereoselectivity (up to 96 4) in the reaction of cis-1,2-disubstituted olefins (136). Extension of this concept to the reaction of a-silyl allyl alcohols also proved feasible and produced the syn (threo) adducts as nearly pure diastereomers (>94 6) (137). Thus, the normal stereoselectivity of the cycloaddition to the Morita-Baylis-Hillman adducts (anti > syn, see above) can be reversed by prior addition of a Grignard reagent (176,177). Both this reversal... 

Nucleophilic addition to carbonyl functionalities undoubtedly represents one of the most important reactions of Grignard reagents. One such reaction is the alkylation of carbon dioxide to give carboxylic acid derivatives. Analogous reactivity is also observed between [TpBu jMgCH3 and CO2. which gives the acetate derivative [Tp ]Mg(f/ -02CCH3) [Eq (6)]. 

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