Thallium amides synthesis

Interestingly, this does not happen during the synthesis of MeSi[SiMe2N(Tl)t-Bu]3. However, it is possible to obtain the partially demetalated thallium amide [MeSi SiMe2N(H)t-Bu SiMe2N(Tl)t-Bu 2] via the controlled thermolysis of MeSi[SiMe2N(Tl)t-Bu]3. ... 

Although one-electron oxidation of arenes by thallium trifluoroacetate presumably does not proceed via formation of a discrete aiylthallium bond, some examples involving oxidative cyclization mediated by thallium trifluoroacetate will be considered here. Schwartz and Hudec employed thallium trifluoroacetate to effect an intramolecular cyclization of the amide (41) to give a key intermediate (42) in their projected synthesis of lycorine alkaloids (Scheme 16). Interestingly, when the bromine was replaced by a hyctogen the yield was poorer. 

Thallium(III) triflate showed also a Lewis catalyst behavior in the synthesis of a-acyloxy ketones. The treatment of ketones in amide solvents followed by addition of small amounts of water cleanly provided the desired product [20]. 

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