2- Iodo-l-methylindole

In a synthesis of polyketides, Kocienski crafted indole 78 from 2-iodo-l-methylindole and the appropriate organozinc reagent 77 derived from the corresponding stannane (76), which itself was reluctant to undergo a Stille coupling [106],... 

Iodo-l-methylindole yields l,l -dimethyl-2,2 -biindole with unactivated copper, whereas with an excess of activated copper, deiodination occurs, together with the formation of a triindolobenzene derivative (80T1439). An analogous reaction occurs upon the addition of copper(I) chloride to l-methyl-2-indolyllithium. It is apparent that only where the formation of the.-2-indolylcopper(I) derivatives is slow, as with deactivated copper on the iodoindole, does the Ullmann reaction between the indolylcopper(I) and the iodoindole occur. It is noteworthy that the 2,2 -biindole system is isolated from the sequential reaction of 1-benzenesulfonylindole with r-butyllithium and copper(I) chloride (80T1439). 

Likewise, quenching the 2-lithro species derived from 6 with CNBr gives 2-bromo-3-iodo-l-(phenylsulfonyl)indole in 80% yield. Lithiation of A-(phenylsulfonyl)indole (3) with LDA followed by quenching with CNBr or benzenesulfonyl chloride gives the corresponding 2-bromo and 2-chloro derivatives in 82 and 93% yields, respectively [15]. Similar lithiation methods have been used to prepare 2-iodo-l-methylindole [16] and l-Boc-2-iodoindole, the latter of which can be converted to 2-iodotryptamine, and its... 

Homoallylic alcohol 1459 was obtained in 64% yield from 5-iodo-l-methylindole 1458 (1.5 mmol), allene (1.0bar) and 4-methoxybenzaldehyde (l.Ommol) (DMF, 80°C, 18h, Schlenk tube) in the presence of indium (100 mesh powder, 1.5 mmol), Pd(OAc)2 (0.1 mmol) and tris(2-furyl)phosphine (0.2 mmol) (Equation 303) <2000CC645>. The use of triphenylphosphine resulted in an incomplete conversion of the starting materials. 

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