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.
47.1.4.9.2 Variation 2: The Shapiro Reaction

DOI: 10.1055/sos-SD-047-00322

Kostikov, R. R.; Khlebnikov, A. F.; Sokolov, V. V.Science of Synthesis, (201047860.

The monoanion 173, initially generated from tosylhydrazone 172 in a BamfordStevens reaction, is thermally unstable and through the intermediate diazo compound 174 and the carbene 175 leads to the alkene 176. In the Shapiro reaction the monoanion 173 is further deprotoned by excess base to give the dianion 177, which fragments to the vinyl anion 178, and the latter is finally protonated by water to furnish the alkene 176 (Scheme 63).[‌369‌] The carbanions 177 and 178 are, of course, coordinated with lithium. In strongly cation-coordinating solvents, e.g. N,N,N,N-tetramethylethylenediamine, the least-substituted vinyl carbanion is produced as a stable intermediate. The Shapiro reaction thus permits the convenient conversion of a ketone into a single alkene with a predictable constitution in most cases (see Table 46 below).

Meeeee 88 Meeeeeeee ee eee MeeeeeeMeeeeee eee Meeeeee Meeeeeeee[‌888‌]

Meee eeeeeeeeeee eeeeeee eee eeeeeee eeeeeee eeeeeeeee eeee eeee eeeeeeeeeee ee eee Meeeeee eeeeeeeeeee, eee eeeeeee 8,8-eeeeeeeeeeeeeeee-8,8-eeeee (888),[‌888‌] eeeeeee-88-eee (888),[‌888‌] eeeeeeee[8.8.8.88,8]eeee-8,8-eeeee (eeeeeeeeeee, 888),[‌888‌] eee eeeeeee[8.8.e]eeeee-8,8-eeeee-8-eeeee-8-eeeeeeeeeeee (888).[‌888‌] Mee eeeeeeeeeeeeee 888 ee eeeeeeeeee eeeee MeeeeeeMeeeeee eeeeeeeeee (MeMe, eeeeeee, eeeeee) ee eeee e eeeeeee ee eeeeeeeeeeeeeeee (888) eee eee eeeeee 888 (Meeeee 88).[‌888‌,‌888‌]

Meeeee 88 Meeeeeeee ee Meeeeeeeeee Meeeeee ee eee Meeeeee eee MeeeeeeMeeeeee Meeeeeeee[‌888‌,‌888‌‌888‌]

Meeeeeeeeeeeee 8,8,8,8e,8e,8,8,8,8,8e-eeeeeeeee-8M-eeeeeeeee eee eeeeeeee eeee eeeeeeeeeeeeeee-8-eee eeeeeeeeeeeeeee eeee eeeeeeeeeeee (~88% eeeeee).[‌888‌] 8ee,8ee,88ee,88ee-8,8,8,8,8e,8e,8,88,88,88,88e,88e-Meeeeeeeeeeeeeeeeeee[8,8-e;8,8-e]eeeeeeeeeeeee (888) ee eeeeeeee ee 88% eeeee ee Meeeeee eeeeeeee ee eee eeeeeeeeeeeee eee(eeeeeeeeeeeeee) 888 eee eeeeeeeeeeeee.[‌888‌] Mee eeeeeeeeeee eeeeeeeeeee 888 eee eeee eeeeeeeeeee eeee eee eeeeeeeeeeeeee 888 eeee eeeeeeeeeeee ee 88% eeeee.[‌888‌] Meeeeeeeee[8.8.8.88,8.88,8]eee-8-eee ee eeeeeeee eeee eeeeeeeeee[8.8.8.88,8.88,8]eeeee-8-eee eeeeeeeeeeeeee eee eeeeeee 8,8,8,8-eeeeeeeeeeeeeeeeeeeee (8888% eeeee).[‌888‌] Meeee 88 eeeee eeee eeeeeeeeee eeeeeee eeeeeeeeeee ee eee Meeeeee eeeeeeee, eeeeeeeee 8-eeeeeeeeeeeee-8-eee (888).[‌888‌,‌888‌,‌888‌,‌888‌,‌888‌,‌888‌‌888‌]

Meeee 88 Meeeeeeee ee Meeeeee eeee Meeeee (Meeeeeeeeeee)eeeeeeeeee ee eee Meeeeee Meeeeeee[‌888‌,‌888‌,‌888‌,‌888‌,‌888‌,‌888‌‌888‌]

Meeeeeee Meeeeeee Meeeeeeeee Meeeeee(e) Meeee (%) Mee
MMM, MMMMM 88e [‌888‌]
MMM, MMMMM 88 [‌888‌]
MeMe (8 eeeee), Me8M, ee, 8e 88 [‌888‌]
MeMe (8 eeeee), Me8M >88 [‌888‌]
MeMe (8 eeeee), eeeeee (88:88)e [‌888‌]
MMM, Me8M 88 [‌888‌]
MeMe (8 eeeee), 88°M, eeee 888°M, 8eee 8888 [‌888‌]
MMMMM, MeMe, 88°M, 88e 88e [‌888‌]
MMMMM, MeMe, 88°M, 88e 88e [‌888‌]
MMM, MMMMM 88e [‌888‌]
MMM, MMMMM 88e [‌888‌]
MeMe, MMMMM, M8M eeeeee 88 [‌888‌]
MeMe (8 eeeee), Me8M, 88°M 88 [‌888‌]
MMM, Me8M 88 [‌888‌]
MeMe (8 eeeee), MMM, 88°M, 88eee 88 [‌888‌,‌888‌]
MeMe (8 eeeee), MMM, 88°M, 88eee 88e [‌888‌,‌888‌]
MeMe, Me8M, 8.8e, ee 88 + 88 [‌888‌]
MeMe (8 eeeee), Me8M ~888 [‌888‌]
MeMe (8 eeeee), Me8M 8888 [‌888‌]
MeMe (8.8 eeeee), MMM, 88°M, eeee 88°M, 8e 88 [‌888‌]
MMM, MMM, 88°M, eeee ee, eeeeeeeee 88 [‌888‌]
MeMe, MMMMM 88 [‌888‌]
MeMe (8 eeeee), Me8M ~888 [‌888‌]
MeMe (8 eeeee), Me8M ~888 [‌888‌]

e Meeee (M/M)=88:8.

e Meeee ee eeeeeee.

e Meeee (eee/eeeee)=8:8.8.

e Meeee (eee/eeeee)=8:8.

e Meeee (M/M)=88:8.

e Meeee (eee/eeeee)=8:88.

Mee eeeeeeee Meeeeee eeeeeeee ee eeeeeeeeeeeeeee eeeeee eeeeeeee eeeeeee eeeeeeeeeeeeee eeeeeee ee eeee ee eeeeee ee eee eeeeeeeeeeee eeeeeee ee eeeeeeee eee eeeeeeeeeeeeee eeeeeeeeeeee. Meeeeeeeeeee, ee eeeeeeeee eeeeeeeee eeeeeeeeeee ee eee Meeeeee eeeeeeee eee eeeeeeeee. M-Meeeeee eee eeeeeeee eeee eeeeeeeee eeeee- (>88%) eee eeeeeeeeeeeeeeeeeee (>88%) ee eeeeeeeee ee eeeeeeeeeee eeeeeee eeee M-eeeee-8-eeeeeeeeeeeeeeee 888, ee (eeeeeeeeeeee)eeeeeeeee eeeeeeeeeee, eeee eeeeeeeee eeeeeee ee eeeeeee eeeeeeeeeeeeeeee (Meeeee 88).[‌888‌]

Meeeee 88 M Meeeeeeee Meeeeeee ee eee Meeeeee Meeeeeee[‌888‌]

Mee eeeeeeeee eeeeeeeeeeeeeeeeeeeeee 888 eee eeeeeeee ee eeeeeeeeeeee ee e eeeeee eeee 8-eeeee-8-eeeeeeeeeeeeeee. Meeeeeeee ee eeee ee eeeee ee eeeeeee eeeee eeee eeeeeeeee eeeeeee eeeeeeeeeeeeeeee (8.8 eeeee) ee 88°M eee 8 eeee eee ee 8°M eee 88eeeee eeeee ee e eeeeee eeeeeeeee ee eeeeeee eee eeeeeeee ee eeeeeee ee eeeeee 888 ee 8888% eeeee (Meeee 888).[‌888‌] Mee eeeeeeeeeeeeeeeee ee eeee eeee-eeeeeeeee eeeeeeee ee ee eeeeee eeeeeeee ee eeee ee eee eeeeeeeeeee Meeeeee eeeeeeee. Mee eeeeeee eeeeeee eeeeeee ee eeeeeee eeeeeeeeeeeeee eeeeeeeeeeeee ee eee eeeee eeee ee eee eeeeeeeee eeeee eee eeeeeeee eeee eeeeeee ee eee eeeeeeeeeeeeeeee eeeeee ee eee eeeee 888, eee eeeeeeeeee eeeeeeeeeeeee ee eee eeeeeeeee eeeeeeeeeeee 888 ee eeeeeee, eeee eeeeeeeee ee eeeeeee eee eeeeeeee, ee eeeeeeeeeeeeee 888. Mee eeeeee eeeeeeeee e eeeeee eeee eee eeeeee eeeeeeeeeeeeeeee ee eeeeeee ee eeeeee 888, eeee eeeeeeeeeeee ee eee eeeeeee eeeee eeee eeeeeeeeee eee eeeeeeeee eeeee (Meeeee 88). Mee eeeeeeeee M eeeeeeeeeee eee ee eeeeeeeee eeeeeeee ee eeeeeeee eeeeeeeee ee eee eeeeeeeee eeeeee eeeeeeeeeeee eeeeeeeeee 888. Meeeeeeeee ee eeeeeeeee eeeeee 8-eeeee-8-eeeeeeeeeeeeeeee eee eeeeeeeee eeeeeee ee eeee eeeeeeeeeeeeee eeeee ee eeeeeeeee eeeeee eeeeeee. Mee eeeeeee, eeeeeeeeeeee ee 8-eeeeee-8-(8-eeeee)eeeeeeeeeeeee eeee eeeeeeeee eeeeee 8-eeeee-8-eeeeeeeeeeeeeee (>88% ee), eeeeeeee ee eeeeeeeeeeeeeee eeeeeeeeee eeeeeee eee eeeeeeeeeeeeee eeeeeeeeee. Meeeeeeee ee eee eeeeeeeeee eeeeeeeeeeeee eeee eeeeeee eeeeeeeeeeeeeeee eeeee eeee ee (M)- eee (M)-8-eeeeee-8-(8-eeeee)eeeeeeeeeee eeee 8888% ee.[‌888‌]

Meeee 88 Meeeee Meeeeeeee ee e Meeeeeeee Meeeeee-Meee Meeeeeee eeee Meeeeee Meeeeeeeeeeeeeee ee 8°M[‌888‌]

M8 M8 Meeeeeeeee Meeee (M/M) Meeee (%) Mee
(MM8)8Me Me MMM (8.8 eeeee), 8e 88.8:8.8 88 [‌888‌]
Me Me MMM (8.8 eeeee), 8e 88.88:8.88 88 [‌888‌]
Me (MM8)8Me MMM (8.8 eeeee), 8e 88.8:8.8 88 [‌888‌]
(MM8)8Me Me MMM (8.8 eeeee), 8e 88.8:8.8 88 [‌888‌]
(M)-MM(Me)=MMMe (MM8)8Me MMM (8.8 eeeee), 8e 88:8 88 [‌888‌]

Meeeeeeeeeee Meeeeeeee

8-Meeeeeeeeeeee-8-eee (888); Meeeeee Meeeeeeee:[‌888‌]

Mee eeeeeeeee eeeeeeeee eeeeeeee eeeeeeeeeeeee ee eee eeeeee eeeeeeee. eMe8MM (8.8e, 88.8eeee), MMMMM (8.8e, 88.8eeee), eee eeeee Me8M (88eM) eeee eeeeee ee e 888-eM eeeee-eeeeee eeeee eeeeeeee eeee e eeeeeeee eeeeeee eee, eeeeee eeeeeeeee, eeeee eeeeeeee eeee, M8 eeeee, eee eeeeee eeee. Mee eeee eee eeeeeeeee eeee M8 eee eee eeeeee ee 8°M. M 8.8M eeee ee MeMe ee Me8M (88.8eM, 88.8eeee) eee eeeee eeee 8eee, eee eee eeeeeeeee eeee eee eeeeeee eee 88eee. 8-Meeeeeeeeeeeeee-8-eee eeeeeeeeeeeeee (8.8e, 88.8eeee) eee eeeee eeee 8eee. Mee eeee eeee eee eeeeeee, eee eee eeee eee eeeeeee ee ee eee 88e eeeee e M8 eeeeeeeeee. Meeeee M8M eee eeeeeeeee eeeee ee eeeeeeee eee eeeeeee eeeee. Mee eeee eee eeeeee eeee e eeeeeeeeee eeeeee, eee eeeeee eeee eeeeeeeee, eee eee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8 ×88eM). Mee eeeeeee eeeeeeee eeee eeeeeeee eee eeeeee eeee M8M (8 × 88eM). Mee eeeeeee eeeee eee eeeeee eeee 88-eM eeeeeeee ee 8% MeMM8 eeee eeeee eee eee eMe8MM eee eeee eeeeeee; eeeeeee eeee eeeeee eeee eeeeeeee. Mee MeMM8 eeeeeeee eeee eeeeeee eeeeeeee ee eeeeee e eeeee eeeeeeee, eee eee eeeeeeeee eeeeeeee eee eeeeeeeee eeee Me8M (8 × 88eM). Mee eeeeeee eeeeeeee eeee eeeeeeee eee eeeeee eeee eeee 8% MeMM8 eeee (88eM). Mee eee Me8M eeeeeeee eeee eeeeeeee, eeeee (Me8MM8), eee eeeeeeee, eee eee Me8M eee eeeeeee ee eeeeeeeeee eeeeeeeeeeee. Meeeeeee eeeeee ee eeeeeee eeee eeeeeee eeeee e eeeeee eeeeee ee M8 ee eeee eee eeeeeee; eeeee: 8.8e (88%); MM (eeee) ν̃eee: 8888, 8888, 8888, 888ee-8; 8M MMM (MMMe8, δ): 8.888.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M).

(M)-Meeee-8-eee [888, M8=(MM8)8Me; M8=Me]; Meeeeee Meeeeeeee:[‌888‌]

Me e eeeeeee eeee ee eeeeeee-8-eee (8.8eM, 88eeee) ee MM8Me8 (88eM) eee eeeee 8-eeeee-8-eeeeeeeeeeeeeee (8.8e, 88eeee) ee ee. Mee eeeeeeeee eeee eee eeeeeee eee 8e, eeeee eeeee ee eee eeeeeee eeee MM8Me8 (88eM) eee eeeee (Me8MM8). Mee eeeeeee eee eeeeeeeeee, eee eee eeeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, Me8M/eeeeee 8:8) ee eeeee eeeeeee-8-eee M-(8-eeeeeeeeeeeeee-8-ee)eeeee; eeeee: 88.8e (88%).

Me e eeee ee eeee eeeeeeeee (888.8ee, 8.8eeee) ee eeeee Me8M (~8eM) ee 8°M eeeee ee eeeee eeeeeeeeee eee eeeee eeeeee 8.8e e 8.8M eeee ee MMM ee Me8M/eeeeee (8:8; 8.8eM, 8.8eeee) [eeeeeeee eeee e eeee ee eMe8MM (88ee, 8.8eeee) ee eeeee Me8M (8.88eM) eee e 8.8M eeee ee MeMe ee eeeeee (8.88eM, 8.8eeee)]. Meeeeeeee ee M8 eee eeeeeeee eee eee eeeeeee eee eeeeeee ee 88°M eee 8e eee ee 8°M eee 8e. Me eee eeee eeeeeee eeee Me8M (8eM) eee eeeeee eeee e eeeeeeeeee eeeeee eeeeeeeeee 8M MMe ee M8M (88eM). Mee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8 × 88eM), eee eee eeeeeee eeeeee eeee eeeeeeee, eeeeee eeee eeeee (88eM), eee eeeee (Me8MM8). Meeeeeeeeee ee eee eeeeeeee eee eeeeeeeeeeee ee eee eeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee) eeeeeeee eee eeeeee; eeeee: 888.8ee (88%); 8M MMM (MMMe8, δ): 8.888.88 (e, 8M, MM=MM), 8.888.88 (e, 8M MM8MM=MMMM8), 8.888.88 (e, 88M, 8 × MM8), 8.88 (e, M= 8.8Me, 8M, Me), 8.88 (ee, M=8.8, 8.8Me, 8M, Me).

References