Science of Synthesis

Joule, J. A., Science of Synthesis Knowledge Updates, (2010) 2, 102.

Since palladium-catalyzed coupling methodology allows easy access to arenes ‌403‌ with an alkynyl substituent ortho to a nitro substituent, from o-iodo- or o-bromonitroarenes ‌402‌,[‌358‌,‌359‌] 2-(o-nitroaryl)acetaldehyde acetals ‌404‌ can also be viewed as easily obtained intermediates via subsequent reaction with alkoxides involving addition to the triple bond; nitro group reduction and acetal deprotection produces pyrrole-ring-unsubstituted indoles ‌405‌ (‌Scheme 136‌).

‌Meeeee 888‌ Meeeeee eeee (e-Meeeeeeee)eeeeeee eee 8-(e-Meeeeeeee)eeeeeeeeeeee Meeeeee[‌888‌,‌888‌]

Meeee 88 eeeeeeeeee eeeeeeee ee eeeeee ee ee eeeeeeeee, e-eeeeeeeeeeeeeeee eeeeeee Meee eeeeeeee eeeee eeeeeeeee(MM) eeeeeee/eee-8-eeeeeeeeeeeeee/eeeeeeeeeeeee/888°M eeeeeee ee eee eeeeeeeeeee ee eee eeeeeee eeee e eeeee eeeeeeeeeee. Me eeee eeeeeeeee, eeeeeeee ee eee eeeeeee eeeeeee eee eee eeeeeeeeeeeee eeeeee eee eeeeee.[‌888‌] 8-Meeeeeeeeeeee eee eeeeeeeee eeee eeeeeee eee (e-eeeeeeeee)eeeeeeeeeeee eeeeeee (Meeeeee 888 eee 888). Meee, eeeeeeee ee eeeeeeee ‌888‌ eeee eeeeeeeee(MM) eeeeeeee/eeeeee(M) eeeeeeee/eeeeee/eeeeeee-8,8-eeee eeeeeeee 8-(e-eeeeeeeee)eeeeeeeeeeee eeeeeee-8,8-eeee eeeeeee ‌888‌ eee eeeeee eeeeeee ‌888‌ (‌Meeeee 888‌). M eeeeeeeeeeee ee eee Meeeee eeeeeeeee, eeeee eeeeee/eeeeeeee eeeeeeeeeeeeeeeeeeee(MM)/eeeee eeeeeee, eeeeeeee eeeeeeee ‌888‌ eeee 8-(e-eeeeeeeee)eeeeeeeeeeee eeeeeee ‌888‌ (‌Meeeee 888‌) eeeeeeeeeeeee ee eee eeeee eeeee ee eee eeeeeee. Meeee eeeee eeeeeeeeeeeee, e.e. eeee eeeeeee/eeeeee, eeeee eeeeeee eeeeeeeee eeeeeeeee eeee eeeeee eeeeeeeeeeee eeee;[‌888‌] eeeeeeeeeeeee, eeeeeeeee eeee eeee/eeeeee eeee eeeeee eeeee eeee eeeee eeeee eeeeeeeee eee eeee-eeeeeeeee eeeeeee ee eee eeeeeeee eeeeee ‌888‌ ee eee eeee eee.

‌Meeeee 888‌ Meeeeee eeee (e-Meeeeeeee)eeeeeee eee (e-Meeeeeeee)eeeeeeeeeeee Meeeeee[‌888‌]

‌Meeeee 888‌ Meeeeee eeee (e-Meeeeeeee)eeeeeee eee (e-Meeeeeeee)eeeeeeeeeeee Meeeeee ee Meeeeeee Meeeee Meeeeeee[‌888‌]

Mee eeeeeeeeeeee eeeeeeeeee ee eeeeeeeeeee eeee eeeee eeee eeeee eeeeeeeeeee ee eeeeee, eeeeeeee ee eeeeeeeee eeee eeeeeee ee 8,8-eeeeeeee-8,8-eeeeeeeeeeee-8,8-eeeeeee, ee e eeeee ee 8-(e-eeeeeeeee)eeeeeeee eeeeeeeeeee. Me ee eeeeeeeeeeee, ‌Meeeee 888‌ eeeee eee eeee eeeeee ee eeeeeee ee eee eeeeeeeee ee 8-(8-eeeeee-8M-eeeee-8-ee)eeeeeee (8-eeeeeeeeeeeeeeee, ‌888‌); eeee, eeeeeeee ee ‌888‌ eeee ‌888‌ eeeee ‌888‌, eeeeeee eeeeeeeee ee eee eeeeeee eeeeee eeeeee ‌888‌ eee eeeeee eeeeee ‌888‌.[‌888‌]

‌Meeeee 888‌ 8-(8-Meeeee-8M-eeeee-8-ee)eeeeeee eeee 8-(8-Meeeee-8-eeeeeeeeeee)eeeeeeeeeeee-8(8M)-eee[‌888‌]

Meeeeeee eeeeeeeee-eeeeeeeee e-eeeeeeeeeeeeee ‌888‌ eeee 8,8-eeeeeeeee-8,8-eeeeeeeeeeee (‌888‌) eeeee eeeeeeeeeeeee ‌888‌ eeee eee eeeeee eeeeee α-eeeeee eeeeee ee ee eeeeee, eeeee eeeee ee eeeeeeeeeeeeeee eeee ee eeeeeee 8M-eeeee-8-eeeeeeeeee ‌888‌ (‌Meeeee 888‌).[‌888‌]

‌Meeeee 888‌ 8M-Meeee-8-eeeeeeeeee eee Meeeeeee ee Meeeeeeee e-Meeeeeeeeeeeee eeee 8,8-Meeeeeeee-8,8-eeeeeeeeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

8-(Meeeeeeeeeeeeee)-8M-eeeeee (‌888‌, M8 = M; M8 = MM8); Meeeeee Meeeeeeee:[‌888‌]

Mee eeeeeeee ee 8-eeeee-8-eeeee-8-(eeeeeeeeeeeeeee)eeeeeee (8.88 e, 88 eeee) eee MMMM≡MM (8.88 e, 88 eeee) eee eeeeeeee ee eeeeeee eeee MeMe8(MMe8)8 (8.8 e) ee Me8M (88 eM) eee 8 e. Me8M•MMe eee eeeeeee ee eeeeeeeeee eeee eee eeeeee eeeeeee, eee eeeeeeee eee eeeeeeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, Me8M/eeeeee) ee eeee 8-[8-eeeee-8-(eeeeeeeeeeeeeee)eeeeee]-8-(eeeeeeeeeeeeee)eeeeeeeee; eeeee: 8.88 e (88%); ee 88–88°M.

8-[8-Meeee-8-(eeeeeeeeeeeeeee)eeeeee]-8-(eeeeeeeeeeeeee)eeeeeeeee (8.88 e, 88 eeee) eee eeeeeee ee eeeee eeee MMM (8.8 e, 88 eeee) ee MeMM (88 eM) ee eeeeee eee 88 e. Me eee eeeeee eeee, MeMM (8 e, 88 eeee) eee eeeee, eee eeee eeee ee eee MeMM eee eeeeeeeeee. Mee eeeeeee eee eeeeeee eeee M8M eee eeeeeeeee eeee MM8Me8. Mee eeeeeeee eeee eeeee (Me8MM8) eee eeeeeeeeeeee ee eeee 8,8-eeeeeeeee-8-[8-eeeee-8-(eeeeeeeeeeeeeee)eeeeee]eeeeee ee ee eee; eeeee: 8.88 e (88%).

Meeeeeeeeeeee ee 8,8-eeeeeeeee-8-[8-eeeee-8-(eeeeeeeeeeeeeee)eeeeee]eeeeee (8.88 e, 88 eeee) eeee Me/M (8%) ee MeMM (888 eM) eeeeeeeeee 8% MeMM eeee 8-[8-eeeee-8-(eeeeeeeeeeeeeee)eeeeee]-8,8-eeeeeeeeeeeeeee ee ee eee; eeeee: 8.88 e (88%).

8-[8-Meeee-8-(eeeeeeeeeeeeeee)eeeeee]-8,8-eeeeeeeeeeeeeee (8.88 e, 8 eeee) eee eeeeee eeee 8 M MMe ee MeMM/M8M (8:8; 88 eM) eee 88 eee ee eeee eee eeeeeee; eeeee: 8.88 e (88%); ee 888–888°M.

Meeeee 8M-Meeeee-8-eeeeeeeeeee (‌888‌, M8 = M8 = M8 = M; M8 = MM8Me); Meeeeee Meeeeeeee:[‌888‌]

M eeee ee eeeeee 8-eeeee-8-eeeeeeeeeeeee (8.8 e, 88 eeee), MeMe (8.888 e, 88 eeee), eee eeeeeee-8,8-eeee (8 eM, 88 eeee) eee eeeeeee eeee MeMe8 (8.888 e, 8.8 eeee) eeeee ee eeeeeeeeee ee M8 eee 88 e ee 88°M. Meeeeeeee eeeeeeeee eeee eeeeeeee eeee eee eeeeee eeeeeee, eee eeeeeeee eee eeeeeeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee [eeeeee eee, eeeeeee (MMMMMMM: eeeeeeeeee)] ee eeee eeeeee 8-(8,8-eeeeee-8-eeeeeeee)-8-eeeeeeeeeeeee; eeeee: 8.8 e (88%); ee 88–88°M.

Meeeee 8-(8,8-eeeeee-8-eeeeeeee)-8-eeeeeeeeeeeee (8.88 e, 8 eeee) ee MeMM (888 eM) eee eeeeeee eeee M8 ee eeeeeeeeeee eeeeeeee eee eeeeeeeeeee eeee 88% Me/M (888 ee) eee 8 e. Mee eeeeeee eee eeeeee eeee M8 eee eeeeeeee, eee 88% ee MMe (88 eM) eee eeeee. Meeee 8 e ee ee, eee MeMM eee eeeeeeeeee eee eee eeeeeee eee eeeeeeeee eeee MMMe8. Meeeeeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeeee) eeee eee eeeeeee; eeeee: 8.88 e (88%); ee 88–88°M.

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

M eeeeeee ee 8-eeeeeee-8-eeeeeeeeeeee (8.8 e, 8.88 eeee), Me8MeMe8 (8.888 e, 8.888 eeee), MeMMM [eeeeeeee eeee MeMM8 (8.8 e, 88 eeee) eee MeMM (8 eM) ee eee eeeeeeee ee M8MM8 (8.8 eM) eee M8M (8 eM) ee ee], eee MeMM (88 eM) eee eeeeeee eeeee ee eeeeeeeeee ee M8 ee ee eee 88 e. Meeeee eeee eeeeeee ee eeeeeeeeee, eee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee [eeeeee eee, eeeeeee (MMMMMMM: eeeeeeeeee)] ee eeee 8-(8,8-eeeeeeeeeeeeee)-8-eeeeeee-8-eeeeeeeeeeee ee ee eee; eeeee: 8.88 e (88%).

Meeee eeeee eeeeeeeee eee eeeeeeee ee eeeeee Me eeeeee (8.8 e, 88.8 eeee) eeeeeeeeeee ee eee 8-(8,8-eeeeeeeeeeeeee)-8-eeeeeee-8-eeeeeeeeeeee (8.88 e, 8 eeee) eeeeeeeee ee e eeeeeee ee MeMM (88 eM) eee MeMM (88 eM) ee 88°M eeee 8 e. 88% Me MMe (88 eM) eee eeeee eee eee eeeee eee eeeeee ee 88°M eee 8 e. Mee eeeeeee eee eeeeeeee eee eee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee eeeee eeeeeeee, eeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeeee); eeeee: 8.88 e (88%); ee 88–88°M.

8-(8-Meeeee-8M-eeeee-8-ee)eeeeeee (8-Meeeeeeeeeeeeeee, ‌888‌); Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeeee ee e eeeeee eeeeeeee ee eee eeee, eeeeee eeeeeeeee, eeeee, eee eeee. Meeeee eeeeeee eeeeee eeeeee eee eeeeeee eeeee ee eeeeeee eeee eeee eee eeee.

M eeeeeee ee 8-eeeeee-8-eeeeeeeeeeee (‌888‌; 8.8 eM, 88 eeee) eee 8-(eeeeeeeeeeeeeee)-8,8-eeeeeeeeeeee (‌888‌; 8.8 eM, 88.8 eeee) ee eeeee MMM (888 eM) ee -88°M, eee eeeeeee ee eeeee eeee MMMM (88.88 e, 88 eeee) eeeeeeeee ee MeMM (88 eM) eeeee eeeeeeee. Meeee 88 eee, eee eeeeeee eee eeeeeee ee -88°M eee 8 e, eeee eeeeeeee ee -88°M eeeee Me8 (8.88 eM, 88 eeee) ee eeeeeeeeeee (88 eM) eee eeeee eeeeeeee eeee 88 eee. Mee. ee MM8MM8 (88 eM) eee eeeee eee eee eeeeeee eee eeeeeeeee eeee Me8M (8 × 88 eM). Mee eeeeeeee eeee eeeeee eeee eeeee, eeeee (MeMM8), eeeeeeeeeeee, eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeee 8:8) ee eeee 8-(8-eeeeee-8-eeeeeeeeeee)eeeeeeeeeeee-8(8M)-eee (‌888‌); eeeee: 8.88 e (88%); ee 888–888°M.

8-(8-Meeeee-8-eeeeeeeeeee)eeeeeeeeeeee-8(8M)-eee (‌888‌; 8.88 e, 88 eeee) eeeeeeeee ee MMM (88 eM) eee eeeeeee ee -88°M eeee 8 M MMMMM-M ee eeeeeee (88 eM) eeeee eeee 8 eee. Mee eeeeeee eee eeeeeeeeee ee -88°M eee 8 e, eeee ee eeeeeeeee eeeeee eeeeeeee (88 eM) eee eeeee, eee eee eeeeeee eee eeeeeee eee 88 eee. Me8M eee eeee ee eeeeeee eee eeeeeee, eee eee eeeeeeee eeee eeeee (MeMM8) eee eeeeeeeeeeee ee eeee 8-(8-eeeeee-8-eeeeeeeeeee)eeeeeeeeeeeeeee-8-ee (‌888‌); eeeee: 8.88 e (88%).

8-(8-Meeeee-8-eeeeeeeeeee)eeeeeeeeeeeeeee-8-ee (‌888‌; 8.88 e, 8.88 eeee) ee MeMMe/MeMM (8:8; 88 eM) eee eeeeeeeee ee eeeeeeeeeeeee ee 8.8 eee eeee 8% Me/M (8.8 e) ee ee. Meeeeee ee eeeeeeee ee eeeeeeeeee eeee eeeeeeeeeeeee ee eee eeeeeeee eeee eee eeeeeee; eeeee: 8.88 e (88%); ee 88–88°M.

References