Conversion of 2-halo-N-allylanilines to indoles via palladium(0) oxidative addition-insertion reactions

Organolithium or Heck type cyclization of N-ortho-iodobenzyl-2-alkenylpyrrolidines to give indolizidines

“…Other reaction conditions, that have been used successfully in related substrates, 5a were tested. Thus, 11b was treated with Pd(PPh 3 ) 4 (5%), n Bu 4 NCl (1.5 eq), NaHCO 3 (2.5 eq), in refluxing CH 3 CN or with Pd(PPh 3 ) 4 (30%), Et 3 N (2.2 eq) in toluene. In these cases a cyclized product could be detected by 1 H NMR spectroscopy of the crude reaction mixtures, but it could not be isolated or characterized, possibly due to instability.…”

“…The combined organic extracts were washed with H 2 O (2 x 10 mL) and sat. NaCl solution (2 x 10 mL), dried with Na 2 SO 4 and evaporated under reduced pressure. The crude product was purified by flash column chromatography (neutral alumina, hexane/AcOEt 50%) to give 9b as an oil (0.297 g, 84% N-(o-Iodobenzyl)-2-vinylpyrrolidine (11a).…”

“…3 The same chemistry with bromide 1 (R = H), palladium acetate (3 mol%) and tris(2-tolyl)phosphine (6 mol%) is known to give (after heating for several days) the product 3 (R = H) in 60% yield (or 87% yield from the iodide). 4 …”

Synthesis of 3‐methyl‐N‐substituted‐1H‐indole

“…As early as 1980, Roy Odle, Burke Blevins and so on have reported the synthesis of some 3-methyl-Nsubstituted indoles, however, they just reported the method of the synthesis without describing optimal reaction condition. [8] As early as 1986, Kasahara and others [9] reported the synthesis of the 3-substituted indole derivatives with 2-halogen phenylamine and a range of allyl compounds, however, palladium catalyst is used in the two-step reactions, and the cost of the reaction is too high, at the same time, there are two active hydrogen that can also be replaced, so the yield of the target product is very low. In 1997, Sansano [10] used organic boron complex, under palladium(0)-catalyzed generation to 1,3-substituted indole, it belongs to Suzuki reaction.…”

Efficient Synthesis of Achiral seco-CI Subunit of Duocarmycin Pharmacophore

“…13,14 Tietze et al 15 and Sakamoto et al 16 also reported that achiral seco-CI was synthesized from 4-methoxy-3-nitroaniline by a Heck reaction in eight steps, respectively.…”