The Stille cross coupling reactions on solid support. Link to solution phase directed ortho metalation. An ester linker approach to styryl, biaryl and heterobiaryl car☐ylic acids

Organotin Reagents in Cross‐Coupling Reactions

“…Malenfant and Fréchet [62] have reported the first solid-phase synthesis of oligothiophenes on a chloromethylated macroporous resin. Couplings of aromatic iodides linked to a polystyrene resin [63] and of the Merrifield resin-linked halobenzoates involving various organotin substrates [64] have been reported. Hermkens and Van Tilborg [65] studied reactions of a Rink amide-bound 4-chloropyrimidine moiety with various organotins; the conditions used were, however, forcing in the extreme (10 equiv.…”

Ruthenium-catalyzed intramolecular cyclization of hetero-functionalized allylbenzenes

“…The solvents were purified according to the literature method, and stored under argon. 2-Allyl-4-methoxyphenol (1b) [13], 1-allyl-2-naphthol (5) [14], 2-(3-methyl-2-butenyl)-4-methoxyphenol (7) [15], 2-(3-butenyl)phenol (9) [16], 2-allylbenzoic acid (11) [17], 2-vinylbenzoic acid (13) [18], 2-allylbenzyl alcohol (17) [19], 2-allylaniline [20], 2-allyl-N-methylaniline [21], N-(2-allylphenyl)acetamide [22], 2-allyl-N-benzanilide [23], 2-allyl-N-tosylaniline (19) [24], and dichloropentamethylcyclopentadienylruthenium dimer [Cp * RuCl 2 ] 2 [11] were prepared according to the literature method.…”

CC Bond‐Forming Reactions

“…Progression in a coupling cycle would further require OH -, CO 3 2-, or F -, not present under the used Stille coupling conditions [178,179]. The Stille conditions proved very useful for affording many aryl-aryl [1,4,180,181,182], vinyl-aryl [9,161,183,184] and also alkyl-aryl [185] compounds bearing hydrolytically labile moieties. The commonly used reactivities of aryl or vinyl halide components are like those in the Scheme 9 Stille coupling: R and R' are aromatic or vinylic residues.…”