Navigation

0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login or sign up for a free trial to access the full content.
20.5.1.6.10 Method 10: Arndt–Eistert and Related Reactions

DOI: 10.1055/sos-SD-020-00757

Phillips, A. J.; Love, C. E.Science of Synthesis, (200720857.

In an analogous vein to the ArndtEistert homologation of acids (see Section 20.2.1.7.4), esters can be homologated by conversion into the diazo ketone, Wolff rearrangement, and trapping with an alcohol. For example, acid 61 is readily homologated by conversion into diazo ketone 62 by reaction of the mixed anhydride with (trimethylsilyl)diazomethane and subsequent treatment with methanol in the presence of silver(I) benzoate to yield methyl ester 63 (Scheme 47).[‌145‌] Histidine-derived diazo ketone 64 can be converted into either the methyl ester 65 (R1=Me) or the benzyl ester 65 (R1=Bn) by employing the appropriate alcohol.[‌146‌]

Meeeee 88 Mee MeeeeMeeeeee Meeeeeeeeeee ee Meeeee eee Meeee Meeeeee[‌888‌,‌888‌]

Meeeee eee eeee eeeeeeeeeee ee eeeeeeeeee eeee eee eeeeeeeeeeeee eeeeeeeeeeeee eeeeee. Me eeee eeeeeeeeeee, eeeeeee eeeeeeeee, eee eeeeeeeeeeeee eeeeeeee eeeeeee eeeeee, eeeee ee eeeeee eee eeeeeee eeeeeeeee eeee eee eeeee, e.e. 88 (Meeeee 88).[‌888‌]

Meeeee 88 Mee MeeeeMeeeeee Meeeeeeeeeee ee Meeeee eee Meeeeeeeeeeee Meeeeee[‌888‌]

Meee eeeeeeee eee eeee eeeeeee ee e eeeeee ee eeeeee, eee eeeeeeeee eeeeeeee eeee ee eeeeeeeee eeeeee ee eee eeeeeeeee (Meeee 8).

Meeee 8 Mee MeeeeMeeeeee Meeeeeeeeeee ee Meeeee eee Meeeeeeeeeeee Meeeeee[‌888‌]

Meeeeeee Meeeeee Meeee (%) Mee
88 [‌888‌]
88 [‌888‌]
88 [‌888‌]
88 [‌888‌]
8888 [‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeee (8M)-8-[(eeee-Meeeeeeeeeeeee)eeeee]-8-(8M-eeeeeeee-8-ee)eeeeeeeee (88, M8=Me; Mee-β-MeeMMe); Meeeeee Meeeeeeee:[‌888‌]

Mee eeeee eeeeee 88 (8 eeeee) eee eeeeeeeee ee MeMM eee eeeeee ee 88°M eeeee eeeee eeee eeeeeeeee ee eeeee. M eeee ee MM8MM8Me (8.88 eeeee) ee Me8M (8.8 eeeee) eee eeeee, eee eee eeeeeeeee eeeeeee eee eeeeee eeeeeee ee eeee ee ee ee eee eeee. Mee eeeeeeee eee eeeeeeeee ee MMM, eee, eeeee eeeeeeeeee (88e), eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Meeee eeeeeeeeeeee eee eeeeeeeee ee eeeeee Me8M (88 eeeee) eee eeeeeeee (8 eeeee) ee eee eeeeeee, eee eee eeeeeee eee eeeeeee eeeee eeeeeeeeee (ee eeeeeeeee, eeeeeee Me8M eee eeeeeeee eeee eeeee). Me eee eeeeeee eee eeeee, ee 8°M, MeMM (8.8eM·eeee8 ee eeeeeeee eeeeeeee), eee eeeeeeee eee eeeeeeeee eee 8e. Mee eeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee, eee eeeeeee eee eeeee ee ee M8M, eee eee eM eee eeeeeeee ee ee. 8 ee eeeeeeee ee eeeee Me8MM8. Meeee eeeeeeeeee eeee MM8Me8 (8 ×), eee eeeeeeee eeeeeee eeeeee eeee eeeee (MeMM8) eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Meeee eeeeeeeeeeeeee eeeeeeee eee eeee eeeeeee; eeeee: 88%.

Meeee Meeeeeeeeeeeeeeee (88); Meeeeee Meeeeeeee:[‌888‌]

M 8.8 M eeee ee MeMe ee eeeeeee (88.8eM, 88.8eeee) eee eeeee ee e eeeeeee, 8°M eeee ee 8,8,8,8-eeeeeeeeeeeeeeeeeeeee (88.8eM, 88.8eeee) ee MMM (88eM) eeee eee-eeee eeeeeee. Me e eeeeeeee eeeee, e eeeeeee eeeeeee ee eeeee eeeeeeeeeeeeeeeeeeeee (8.8e, 88.8eeee) eee MM8Me8 (8.88eM, 88.8eeee) ee MMM (88eM) eee eeeeee ee 88°M eeee e eee eee/eeeeeee eeee. Meeee 88eee, eee MMMM eee eeeeee eeee e eee eee/eeeeeee eeee eee eeeee eeee e 88-eee eeeeee eee e eeeeee-eeeee eeeeee ee eee eeeee eeeeeee ee e eeeeeeeeeee eeeee 88°M. Meeee 88eee, e eeeeeee eeeeeeee 88°M eeee ee MeMMMM [eeeeeeeee eeeeeeee ee 8°M eeee (MMM)8MM (88.8eM, 88.8eeee) eee 8.8 M MeMe ee eeeeeee (88.8eM, 88.8eeee) ee MMM (88eM)] eee eeeee eeee e 88-eee eeeeee ee e eeeeeeeeeee eeeee 88°M. Mee eeeeeee eee eeeeeee ee eeee ee 88°M eee eeee eeeeeeee ee 88°M, eee e eeee ee e-MeMe ee eeeeeeeeeee (88.8eM, 888.8eeee) eee eeee eeeee eeee e 88-eee eeeeee ee e eeeeeeeeeee eeeee 88°M. Mee eeeeeee eee eeeeeee ee eeee ee 88°M, eee e 8.8 M eeee ee MeMe ee eeeeeee (88.8eM, 88eeee) eee eeeee. Mee eeeeeee eee eeeeee ee ee eee eeeeeee eee 88eee. Mee eeeeeee eee eeee eeeeee ee 88°M eee eeeeeeee eeee ee 88-eee eeeeee eeee e eeeeeee eeee ee eeeeee MeMM (888eM) ee 8°M. Mee eeeeeee eee eeeeeee eeee Me8M (888eM) eee eeeeee eeee 88% ee MMe (888eM). Mee eeeeeee eeeee eee ee-eeeeeeeee eeee Me8M (8 × 888eM), eee eee eeeeeeee Me8M eeeeee eeee eeeeee eeee eeeee eee eeeee. Mee eeeee eeeeeee (8.88e) eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeee 8:88) ee eeeeee eee eeeee; eeeee: 8.88e (88%).

References


Cookie-Einstellungen