Manganese mesylates

Functionalized benzylic mesylates containing a halogen atom were also investigated. Reactions of the halogenated benzyl manganese mesylates with acid chlorides, aldehydes, and ketones yielded the corresponding ketone, secondary alcohol, and tertiary alcohol in good to excellent isolated yields as shown in Table 8.11. As mentioned earlier, it is of interest that the mesylates... 

Typical Procedure for the Cross-Coupling Reactions of Benzyl Manganese Mesylates... 

Benzylmanganese sulfonates. A preparation of the.se reagents is by direct reaction if tosylates and mesylates with Rieke manganese in THF at room temperature. They tsehave similarly to Grignard reagents. 

The closure of the D-ring succeeded under basic conditions via an 8 2 displacement of the mesylate by the secondary amine (Scheme 16). Morphinan 106 was then successfully converted into thebaine (3) via manganese dioxide mediated oxidation following a procedure by Rapoport [67]. 

We reported that Mn does, in fact, undergo oxidative addition to alkyl and benzylic tosylates and mesylates under mild conditions to yield the corresponding organomanganese tosylates and mesylates in excellent yields. To our knowledge, this is the first example of organomanganese tosylates and mesylates prepared via direct oxidative addition of manganese metal or by any metathesis approach. 

Benzyl mesylate (9 mmol) was added via a syringe to the slurry of active manganese (lOmmol) being stirred in THF (10ml) at rt. The resulting mixture was stirred at rt for 20 min. The reaction was monitored by gas chromatography. 

The following is a representative procedure to a slurry of Rieke manganese (10.0 mmol) in THF (10 ml) under argon was added benzyl mesylate... 

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