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15.5.1.1.1.2.3.2.6 Variation 6: Using Carbonyl Component Synthons

DOI: 10.1055/sos-SD-015-01146

Álvarez, M.; Joule, J. A.Science of Synthesis, (200515684.

A range of precursors for the Mannich electrophile in the PictetSpengler-type closure have been employed in special situations. These include the protonation of en­amines[‌75‌‌78‌] and enamides,[‌79‌] and the release of the carbonyl group from an acetal,[‌80‌] an enol ether,[‌80‌] or a chloromethyl methyl ether.[‌81‌] One sequence[‌82‌,‌83‌] uses a glycidate 90 in lieu of an arylacetaldehyde, thus avoiding the complications associated with the aldehyde in the presence of the acid required for the ring synthesis, e.g. in the synthesis of 91 and 92 (Scheme 40).

Meeeee 88 MeeeeeMeeeeeee Meeeeee Meeee e Meeeeeeee[‌88‌]

M,M-Meeeeee 88 eeeeeeee eeee eeeeee eeee 8-eeee-M-eeeeeeeeeeeeeeeee 88 ee eeeeeeee eeee ee eeeeeeee, eeeeeee, eee eeeeeeeee eeeeeeeee, eee eeeeee eeee eeeeee, eeeeeeeeee eeee e eeee eeeeeeee-eeee eeeeeeee eeee, eeeee eeee eeeeeeeeee eeeee eeeeeeeeeeeeeee eeee ee eeee eeeeeeeeeee ee eeee 8,8,8,8-eeeeeeeeeeeeeeeeeeeeeee 88 (Meeeee 88).[‌88‌]

Meeeee 88 MeeeeeMeeeeeee Meeeeee Meeee M,M-Meeeeee ee Meeeeeee Meeeeeeee Meeeeeee[‌88‌]

8-Meee-M,M-eee(8M-eeeeeeeeeeee-8-eeeeeeee)eeeeeeeeeee 88 eee eeee eeeeee eeeeeeee, eee ee eeeeeeee ee eeeeeeee eeeeeeeeeee, eeeeeeee eeeeeee eeeeeee eeeee eeee eeeee ee eeee 8,8,8,8-eeeeeeeeeeeeeeeeeeeeeee 88, eeee ee ee eeeeeeeeee eeeeeeeeeee eeeee (Meeeee 88).[‌88‌] Mee 8-eeeeeeeeeeeeeeeeeeee eeeeeeeeeee ee eee eeeeeee eee ee eeeeeee eeee eeeeeeeeeee ee eeee e 8-eeeeee eeeee eee eeeeeeeeee eeeee eeee ee eeeeeeeee ee eeee eeeeeeeeeee eeeeeeeeeeee eeeeeeeeeeeee.

Meeeee 88 MeeeeeMeeeeeee Meeeeee Meeee 8-Meee-M,M-eee(8M-eeeeeeeeeeee-8-eeeeeeee)eeeeeeeeeee[‌88‌]

Mee eee ee ee eeeeee ee e eeeeeeee eeeeeee ee eeeeeeee ee eeeee e eeeeeeee eeeeeeeeeee 88 ee e eeeeeeee eeee eeeee ee eeee eeeeeeeeeeee eeeeeee (Meeeee 88). Mee eeeeeee ee eeeeeeeeeee ee eeee-Meeeeeeeeee eeeeeeeeeeeeee eeeeeeeeeeeeee; eee eeeee 88 ee eee eeeeeeee eee eeeeeee eeee eeee ee eeeeee eeee eeeeeee ee eee 8,8,8,8-eeeeeeeeeeeeeeeeeeeeee 888.[‌88‌]

Meeeee 88 Meeeeeeee ee e MeeeeeMeeeeeee Meeeeeeeeeee eee Meee-Meeeeeeeeee Meeeeeeeeeeeee ee ee Meeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeee (8M,8M)-8-(8,8-Meeeeeeeeeeeeee)-8,8-eeeeeeeee-8,8,8,8-eeeeeeeeeeeeeeeeeeeeee-8-eeeeeeeeeee (88) eee Meeeee (8M,8M)-8-(8,8-Meeeeeeeeeeeeee)-8,8-eeeeeeeee-8,8,8,8-eeeeeeeeeeeeeeeeeeeeee-8-eeeeeeeeeee (88); Meeeeee Meeeeeeee:[‌88‌]

M eeeeeee ee eeeeee 8-(8,8-eeeeeeeeeeeeeee)eeeeeeeee (8.8e, 88eeee) ee M8M (88eM) eee 8-(8,8-eeeeeeeeeeeeeee)-e-eeeeeee eeeeee eeeee eeeeeeeeeeeee (8.8e, 88eeee) ee MeMM (88eM) eee eeeeeeee ee eM 8 eeee MeMM eee eee eeeeeee eee eeeeeee ee 88°M eee 88e. Meeee eeeeeeeeeee ee MeMM, MeMMe eee eeeee, eee eeeeeee eeeee eeeeeeeee eeee 88% ee MMe eee eee eeeeeeee eeeeeee eeeeeeee eeeeeeeeeee eeee M8MM8 eee eeee eeeeeeeee eeee MeMMe. Mee eeeeeee eeeeeeee eeee eeeeee eeee M8M, eeeee, eee eeeeeeeeee eee eee eeeeeeeee eee eeeee eeeeeee eee eeeeeeeee ee eeeeeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, MMMe8/MeMMe 8:8). Meeeeeeeeeeeeee (MeMMe/eeeeee) eeee eeeeee (8M,8M)-8-(8,8-eeeeee­eeeeeeeee)-8,8-eeeeeeeee-8,8,8,8-eeeeeeeeeeeeeeeeeeeeee-8-eeeeeeeeeee (88); eeeee: 8.8e (88%); ee 888888°M eee eeeeeeeeeeeeeee (MeMMe/MMMe8) eeee eeeeee (8M,8M)-8-(8,8-ee­eeeeeeeeeeeee)-8,8-eeeeeeeee-8,8,8,8-eeeeeeeeeeeeeeeeeeeeee-8-eeeeeeeeeee (88); eeeee: 8.88e (88%); ee 888888°M.

8-Meeeee-8,8,8-eeeeeeeeee-8-eeeeee-8,8,8,8-eeeeeeeeeeeeeeeeeeeeee (88, M8=M); Meeeeee Meeeeeeee:[‌88‌]

M eeee ee M-eeeeee-8-(8,8,8-eeeeeeeeee-8-eeeeeeeeeeee)eeeeeeeeee (888ee, 8.8eeee) eee eeeee M8MM8 (888ee, 8eeee) ee MeMM (8.88eM) eee eeeeeee eee 88eee ee ee. Meee­eeee­eeeeeeee (88ee, 8eeee) eee eeeee eee eee eeeeeee eeeeeee eeeeeeeee ee ee. Mee eeeeeee eee eeeeeeee eee eee eeeeeeee eeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee eee eeeeeeee M,M-eeeeee 88 (M8=M) ee e eeeee, eeeee eee eeee eeeeeee eeeeeee eeeeeeeeeeee ee eeeeeeeeee ee MMM (8eM). Meeee 8e ee ee eee eeee eee eeeeeeeeeeee eee eeeeeee eeee M8M (88eM), eeee eeeeeeee eeee eee. ee MeMMM8 eee eeeeeeeee eeee MMMe8 (8×88eM). Mee eeeeeeee eeeeeeee eeee eeeee eee eeeeeeeeee ee eeee eeeeeeee eeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, MM8Me8) eeeeee e eeeeeeeee eee; eeeee: 888ee (88%).

8-(8M-Meeeeeeeeeee-8-eeeeeeee)-8-eeeeee-8,8,8,8-eeeeeeeeeeeeeeeeeeeeee (88, M8=8-Me); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeeee eeeeeeeeeee eeee ee e eeeeee eeeeeeee ee eee eeeeeee eee eeeeee eeeeeeeee eeee eeeee.

8-(8-Meeeeeeeeeee)eeeeeeeeee (8.88e, 88.8eeee) eee 8-(eeeeeeeeeeeee)-8M-eeeeeeeeeeeee (8.88e, 88.8eeee) eeee eeeeee eeeeeeee ee eeeeee ee eeeeeeeeee MeMM ee eeeeeeee eee eeeeeeeee, eee 8e. Mee eeeeeee M,M-eee(eeeeeeeeeeeeeeeeeeee) eeeeeeeeee 88 (M8=8-Me) eeeeeeeeeeee eee; eeeee: 8.88e (88%); ee 888888°M. M eeeeeee (8.88e, 8.8eeee) ee MMMe8 (88eM) eee eeeeeee eeee MeMe8 (8.88e, 88.8eeee) ee ee, eeee eeeeeeee, eee 8e. Mee eeeeeee eee eeeeee eeee eeeeeee eee eee 8M MeMM (88eM) eeeee ee eeeee eee eM ee 88. Mee eeeeee eeee eeeeeeeee eee eee eeeeeee eeeee ee-eeeeeeeee eeee MMMe8 (8×88eM). Mee eeeeeeee eeeeeeee eeee eeeeeeee eeee ee MeMM, eeeee, eeeeeeee, eee eeeeeeeeee; eeeee: 8.88e (88%); ee 888888°M.

8,8-Meeeeeeee-8-eeeeee-8,8,8,8-eeeeeeeeeeeeeeeeeeeeee (888); Meeeeee Meeeeeeee:[‌88‌]

Me e 88-eM Meeeeee eeee, eee(eeeeeeeeeeee)eee[M-(8,8-eeeeeeeeeeeeeeeee)eeeeeeeee-κM,κM]eeeeeeee (88; 88ee, 8.88eeee), 8-(8,8-eeeeeeeeeeeeeee)eeeeeeeeee (888ee, 8.8eeee), eee-8-eee (88ee, 8.8eeee), eee eeeeeee (8eM) (MMMMMMM: eeeeeeeeee) eeee eeeeee ee 88°M eee 88e. Mee eeeeeee eee eeeeee eee MMM (8eM) eeeee eee eee eeeeeee eeeeeeee eee 88e. Mee eeeeee eeeeeee eee eeeeeee eeee eee. MeMMM8 (888eM) eee eeeeeeeee eeee Me8M. Meeeeee eee eeeeeee eeee eee eeeee eeeeeee eee eee eeeeeee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, MM8Me8/MeMM 88:8), eeeeee eee eeeeeeeeeeeeeeeeeeeeee 888 ee ee eee; eeeee: 888ee (88%).

References


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