Addition of O-H Bonds across Alkenes and Related Reactions

2 Addition of O-H Bonds across Alkenes and Related Reactions 

From the beginning of the 1970s until the mid 1980s, several examples of the telomerization of dienes with water [76, 77] or methanol [78, 79] to isomeric mixtures of dienols or dienol ethers catalyzed by palladium-phosphine complexes in the presence of carbon dioxide have been reported. Neither the yield nor the selectivity were very high. However, when allene was employed as a diene , 3-methyl-2-meth-ylene-3-buten-l-ol was obtained with fairly good selectivity (up to 98%) (Eq. 6.43) [78]. 

The Co2(CO)g/pyridine system can catalyze carbomethoxylation of butadiene to methyl 3-pentenoate (Eq. 6.44) [80]. The reaction mechanism of the cobalt atalyzed carbalkoxylation of olefins was investigated and the formation of a methoxycar-bonylcobalt species, MeOC(0)Co from a cobalt carbonyl complex with methanol as an intermediate is claimed [81,82]. 

Efficient anti-Markonikov addition of water to terminal olefins producing primary alcohols would be one of the most desirable catalytic processes (Eq. 6.45). As one example of such a reaction, Jensen and Trogler reported the anti-Markonikov hydration of terminal olefins catalyzed by a platinum(II) trimethylphosphine complex producing primary alcohols [83]. The report, however, was claimed to be of doubtful reproducibility [84]. 

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