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[ P r e s e n t s ]
Ah, our old friend Sandmeyer
Palladium-catalyzed reactions in the synthesis of 3- and 4-substituted indoles. Approaches to ergot alkaloids
Peter J. Harrington, Louis S. Hegedus;
J. Org. Chem.; 1984; 49(15); 2657-2662.
(
http://pharmacist-hive.tripod.com/4-subst-indol-ergot.pdf)
Abstract: An efficient synthesis of 4-bromo-1-tosylindole (10) based on the Pd(II)-catalyzd cyclization of an o-ethenylaniline p-toluenesulfonamide has been developed. A Pd(0) oxidative addition-olefin insertion-B-hydride elimination cycle converted 10 to a number of 4-substituted 1-tosylindoles. Selective electrophilic substitutions at the 3-position of 10 provided access to the 3-(chloromercurio)- (18) and 3-iodo-l-tceylindoles (22). Transmetalation to palladium and allyl chloride insertion converted 18 to 3-allyl-4-bromo-1-tosylindole (20) which could be cyclized to the benz[c,d]indoline 21. A Pd(0) oxidative addition-olefin insertion-@-hydride elimination cycle converted the 3-iodo compound 22 to a number of 4-bromo-3-substitutd 1-tosylindoles including 24, a potential precursor to optically active tryptophans.
Fellow tryptamine bees, enjoy and expect more on 4-subst indoles!