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DOI: 10.1055/sos-SD-110-00001

Joule, J. A.Science of Synthesis Knowledge Updates, (2010241.

There is a group of indole syntheses which are mechanistically analogous to the Fischer in the crucial 3—3a bond-forming step (122 to 123), but which utilize O-alkenyl-N-arylhydroxylamines 122 (Scheme 47) instead of the ene–hydrazine tautomer of arylhydrazones. Access to O-alkenyl-N-arylhydroxylamines is not as straightforward as to the substrate arylhydrazones of the Fischer sequence; however, their pericyclic rearrangements proceed at much lower temperatures. The rearrangements lead to α-(o-aminoaryl) ketones 124 (see also Section in which amine-to-carbonyl addition (to give 125) followed by loss of water gives the aromatic indole 126.

Meeeee 88 Meeeeee eeee M-Meeeeee-M-eeeeeeeeeeeeeeeeee; Meeeeee Meeeee

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Meeeee 88 8,8-Meeeeeeeeeeee 8-Meeeeeeeeee eeee M-Meee-M-eeeeeeeeeeeeeeeeee eee Meeee Meeeeee[‌888‌,‌888‌]

M-Meee-M-(eeeeeeeeeeeeeeeee)eeeeeeeeeeeeee, e.e. 888, eeeeeee eeeeeeee ee eeeeee eeeeeeeeee ee eeee eeeeeee, e.e. 888, eeeee eeeeeee eeeeeeeeeee eeeeeeeeeeeee eeeeeeeeeeeee eeeeeee, eeeee eeeeeee ee eee eeeeeee eeee, ee eeeeee-8-eeeeeeeeee eeee eeeeee, e.e. 888 (Meeeee 88).[‌888‌] M-Meeeeeeeeeeeeeeeee eeeeeee eeeeeeee ee eeeeeeee eeeeeeeeeeeeeeeee­eeeee eee eee eeeeeee eee eeeeeeeeeee eeee eeeeee-8,8-eeeeeeeeeeee eeee eeeeeeeeeee.[‌888‌]

Meeeee 88 M Meeeee 8M-Meeeee-8-eeeeeeeeeee eeee ee M-Meee-M-(eeeeeeeeeeeeeeeee)eeeeeeeeeeeee eee Meeeee Meeeeeeeee[‌888‌]

Mee eeeeeeee ee [8-(eeeeeeeeeeeeee)eeeee]eeeeeeeee eeeeeee (888) eeee eeeeeeeeeeeee 888 ee eeeeeee ee eeeeeee eeeeeee eeeeeeee ee eee eeeeee ee eee eeeeeee eeeee eeeeeeeee 888 eee ee eeee eeeeeee eeeee eee eee eeeeeeeeee ee M-eeeeeee-M-eeeeeeeeeeeeeeeeee; 8-(eeeeeeeeeeeeee)-8M-eeeeeee 888 eee eee eeeee eeeeee ee eeee eeee (Meeeee 88).[‌888‌]

Meeeee 88 8-(Meeeeeeeeeeeee)-8M-eeeeeee eeee Meeeeeeeeeeee eee Meeee Meeeeeee Meeeeeee[‌888‌]

Mee eeeeee eeeee 888 ee M-eeeeeeeeeeeeeeeeee eeeee ee eee eeeeeee eeeeee eeee eeeeeee eeeeeeee eeeeeeee-eeeeeeeeeee eeeeeeeeeeee M, eee eee eeeeeeeee eeeeeeeeeeeee 888 eeeeeeeee ee eeee eeeeeee 888 (ee. Meeeeee eeeee ee-eeeeeeeeeeeee, eeeee ee eeeeeee ee eeeee eeeeeeeee eeee eeee ee 8-eeeeeeeeeee eeeeeee 888 (Meeeee 88).[‌888‌]

Meeeee 88 8-Meeeeeeeeee Meeeeee eeee Meeeeeeee M-Meeeeeeeeeeeeeeeee eee Meeeeee Meeeeeee Meeeeeee-Meeeeeeeeee Meeeeeeeeeee[‌888‌]

M eeeeee eeeeeeeee ee 8-eeee-8M-eeeeeee 888 eeeeeee eeee eee eeeeeeeeeee ee M-eeeeeeeeeeeeeeeeee eeee ee 888 eeee eeeeeee (Meeeee 88).[‌888‌] Mee eeeeeeeee eeeeeeee e 88 eee% eeee(MM) eeeeeeeeeeeeee [Me(Me)] eeeeeeee. Me ee eeeeeeee eee ee eeeeeee eeeeeeeee eeeeeeee ee eee eeeeeeeeeeeee ee eee eeeeee, eee eeeee e eeeee eeee eeee eeeeeeeee ee eee eeeeeeeee ee eeee eeeeeee (Meeeee 88), eee eeeeee eeeeeeeee ee eeeeeeeeeeeee ee eeeeeee eee eeeeeeeeeee ee eeee eeee eee eeeeee.

Meeeee 88 Meeeeeee ee Meeeeeeeeeeeeeeeee eee Meeeeee Meeeeeeee ee Meee(MM) Meeeeeeeeeeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 Meeee (%) Mee
Me Me 88 [‌888‌]
8-MeMM8M8 M 88 [‌888‌]
8-eeeeeee M 88 [‌888‌]
8,8-(MeM)8M8M8 M 88 [‌888‌]

Meeeeeee 888 eeeeeeee ee eee eeeeeeee ee ee M-eeeeeeeeeeeeeeeee eeee ee eeeeeeee, eeeeeee eeeeeeeeeeeee ee eeeeeee 888 eeeeeeee eeeeeeee-eeeeeeeeeee eeeeeeeeeeee, eeeeeeeee eeeeeeeeeeeeee 888 eee eeeeeeeeee 8-eee-8-eeeeeeeeeee 888 eeeeeee eeeeeeeeeeeee 888 eee 888 ee eeeee (Meeeee 88).[‌888‌‌888‌]

Meeeee 88 8-Mee-8-eeeeeeeeeee eeee Meeeeeeeeeee eee Meeeeee Meeeeeee Meeeeeee-Meeeeeeeeee Meeeeeeeeeee[‌888‌‌888‌]

Mee eeeeeee M-eeeeeeeeeeeeeeeee eeeeeee eeeeeeee, ee e eeeee eeee, M-eeeeeeeee ee ee M-eeeee-M-(eeeeeeeeeeeee)eeeeeeeee 888 eee eeee eeeeeeeeeeeee ee eee M-eeeee 888 ee eeeee (Meeeee 88) ee eee M-eeeeeee-M-eeeeeeeeeeeeeeeee eeeeeeeeeeee 888 eee e eeeeee eeeeeeeeee eeee eeeeee eee 8—8e eeee eee eeeeeee e 8-eeeee-8M-eeeeee 888.[‌888‌]

Meeeee 88 8-Meeee-8M-eeeeeee eeee M-(Meeeeeeeeeeee)-M-eeeeeeeee M-Meeeee[‌888‌]

M-(Mee-8-eeee)eeeeeeeeee 888 eeeee eeee 8-eeeeeeeeeeeeeeeeeee eeee ee eeee eeeeeee ee eeeee eee eeeeeee eeeeeee ee eeeeeeeeeeee ee e eeeeeeeeeee eeee e (8-eeeeeeeeeeee)eeeeeeeeeeeeeeeee ee eee eeeeeee eeeeeee.[‌888‌] Mee eeeeeeeee ee eeeee eeeeeeeeeeee eeeeee eeee ee eeeeeee eee, eeee, eeee eee eeeeeeeeeeeee eeeeeeeeeeee ee eeeeeeeeeee eeee eeeeeee, eeeeeee 8M-eeeee-8-eeeeeeeeeeeeeee 888 ee Meeeee 88.[‌888‌] Mee eeeeeee eee eeeeeeeeeeee (Meeeee 88) ee eeeeeeee eeeeeee M-eeeeeeeee (ee 888), eeee eeeeeeeeeeeeee (eeeeee ee 888) ee ee eeeeeeeee 888 eeeee eeeeeeeee e eeeeee eeeeeeeeeeeee eeeeee 888 eee eeee eee eeeeeeeeee eeeeeee 888; eeeeee-eeeeeeeee eeee ee eeeee eeee 888 eeeeeeee e eeeeeee 888 eeeee eee ee eeeeeeeeeee eeee ee eeeeee 888 ee eee eeeeeeee ee e eeeeeeeeeee (eeeeee ee 888).

Meeeee 88 8M-Meeee-8-eeeeeeeeeeeeeee eee M-Meeeeeeee ee M-(Mee-8-eeee)eeeeeeeeee[‌888‌]

Meeeee 88 Meeeeeeee eee Meeeeeeee ee Meeeeee ee M-Meeeeeeee ee M-(Mee-8-eeee)eeeeeeeeee

Meeeeeeeeeee Meeeeeeee

8-Meeeee-8M-eeeeee (888, M8 = Me; M8 = M8 = M8 = M); Meeeeee Meeeeeeee:[‌888‌]

M eeeeeee ee M-eeeeeee-M-eeeeeeeeeeeeeee (88.8 e, 8.8 eee), Me8MeMe8 (8 e, 8.8 eeee), eee eeeee eeeeeee (888 e, 8.8 eee) eeee eeeeee eeeeeeee ee 88°M eee 8 e. Mee eeeeeee eee eeeeee eeee 88% eeeee, eeeee, eee eeeeeeeeeeee, eee eeeeeee eeeee eeeeeeee ee eeeeeeeeee (eeeeee eee, eeeeeee/MeMMe 8:8) eee eeee eeeeeeeeeeee (ee 888–888°M/8888 Me), eeeeee eee eeeeeee ee ee eee; eeeee: 88.8 e (88%).

Meeeee 8-(Meeeeeeeeeeeeeeee)-8-eeeeeee-8M-eeeeee-8-eeeeeeeeeee (888); Meeeeee Meeeeeeee:[‌888‌]

Me e eeeeeee eeee ee eeeeee M-eeeeeee-M-(8-eeeeeeeeeeeee)eeeeeeeee (8.88 e, 8.8 eeee) eee eeeeee eeeeeeeeee (8.8 eM, 88.8 eeee) ee eee MM8Me8 (88 eM) eee eeeee 8-eeeeeeeeeeeeeeee (8.88 eM, 8.8 eeee). Me eee eeeeeeee eeeeeeeee, eee eeeeeeeeeee eeee ee 88°M; eeeee 8 e, eee eeeeeee eee eeeeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, MM8Me8/eeeeee 8:8) ee eeee 888, eeeee eee eeeeeeeeeeeeee (MeMM); eeeee: 8.88 e (88%); ee 888°M.

8-(Meeeeeeeeeeeee)-8M-eeeeee (888, M8 = M8 = M8 = M8 = M); Meeeeee Meeeeeeee:[‌888‌]

Me e eeeeeeeeee eeeeeee, M8-eeeeeee eeee ee [8-(eeeeeeeeeeeeee)eeeee]eeeeeeeee eeeeeee (8.88 e, 88 eeee) ee Me8M ee -88°M eee eeeee eeeeeeee eeeeeeeeeeeeee (8.88 e, 8 eeee) ee Me8M (88 eM). Meeee 88 eee, eee eeeeeee eee eeeeeee ee eeee ee 8°M eee eeeeeeeeee ee eeee eeeeeeeeeee eeeeeeeee, eeee eee eeeeeee eee eeeeeeeee eeee Me8M eee eee eeeeeee eee eeeee (Me8MM8) eee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, Me8M/eeeeeeeee eeeee 8:8) ee eeee eee eeeeeee ee ee eee; eeeee: 88%.

(8-Meeeee-8-eeeeee-8M-eeeee-8-ee)eeeeeeeeeeee (888, M = MM; M8 = Me; M8 = Me); Meeeeee Meeeeeeee:[‌888‌]

M-Meeeeee-M-(8-eeeee)eeeeeeeee (8.88 e, 8 eeee) ee eeeee MMM (88 eM) eee eeeeeee eeee MeM (88% eeeeeeeeee ee eee, 8.88 e, 8 eeee) ee ee eee 88 eee. Mee eeeeeeeee eeeee eee eeeeeee eeee eee eeeeeee eeeeeeeeeeeeeeee (8.88 e, 8 eeee) eee eeee-8,8-eeeeeeeeeeee (8.88 e, 8.8 eeee). Meeeeeeeeeeeee ee eeeeeeee ee MMM8M eee M8M (888 eM) eeeeeeee ee eeeeeeeeee eeee MM8Me8, eee eeee eeeeeeeeeeeee eeee 8-[8-eeeeeeeee-8-eeeeeeeeeeee]-8-eeeeeeeeeeeeeeee, eeeee eee eeeeeeeeeeee (MMM); eeeee: 8.88 e (88%); ee 888–888°M.

8-[8-Meeeeeeee-8-eeeeeeeeeeee]-8-eeeeeeeeeeeeeeee (8.88 e, 8 eeee) eee eeeeee ee MMM8M (8 eM) eee 88 eee ee 88°M. Mee eeeeeee eee eeeeeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeeeeeee (Me8M/MeMMe) ee eeee eee eeeee eeeeeeee; eeeee: 8.8 e (88%); ee 888–888°M.

8-(8,8-Meeeeeeeeeeeeee)-8M-eeeeee [888, M8 = 8,8-(MeM)8M8M8; M8 = M]; Meeeeee Meeeeeeee:[‌888‌]

M eeeeeee ee Me(Me) (88 ee, 8.88 eeee), (8,8-eeeeeeeeeeeeeee)eeeeeeeee (8.88 e, 8.8 eeee), eee eeeeeee (88 eM) eee eeeeeee ee eeeeee eeeee eeeee eee ee eeee eee eeeee M-eeeeeeeeeeeeeeeeeee (888; 88 ee, 8.88 eeee) ee eeeeeee (8 eM) ee eeeeeee eeee (8–8 e). Meeee eee eeeeeeee eee eeeeeeee, eeeeee eee eeeeeeeee eeeeeeeee (8–88 e). Meeee eeeeeee, eee eeeeeee eee eeeeeeeeeeee ee e eeeee eeeee eeeeeee eeeeeeee. Meeee eeeeeeeeeeeeee ee eee eeeeeee (eeeeee eee, MeMMe/eeeeee 8:8) eeeeeeee eee 8M-eeeeee ee e eeeeee eeeee; eeeee: 88.8 ee (88%).

8-(8M-Meeee-8-ee)-8-(8-eeeeeee)eeeeeeeeeeeee (888, M = MM; M8 = 8-Meeeeee; M8 = M); Meeeeee Meeeeeeee:[‌888‌,‌888‌]

M-Meeeeeeeeeeeeeeeeee (8.88 e, 8 eeee) eee eeeeeeeee-8-eeeeeeeeeeee (8.88 e, 8 eeee) eeee eeeeeee ee MeMM (88 eM) eeeee MMM eeeeeeeeee eeeeee eeeeeeee eeeeeeeeee eeee eeeeeee. Meee-8,8-eeeeeeeeeeee (8.88 e, 88 eeee) eee eeeee eee eee eeeee eee eeeeee ee 88°M eee 88 eee. Meeeeeeeeeeee eee eeeeeeeeeeee ee eee eeeeeee ee eeeeeeeeeeeeeee (Me8M) eeee eee eeeeeee; eeeee: 888 ee (88%); ee 888°M.