0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via Variation 4: Styrenes, 1,3-Dienes, and Alkynes

DOI: 10.1055/sos-SD-008-00003

Dieter, R. K.Science of Synthesis, (20068101.

Although infrequently used in synthesis, styrene double bonds (Table 18)[‌465‌] and conjugated 1,3-dienes[‌466‌] (Table 19) are readily reduced with dissolving metals in the presence of proton donors.[‌9‌] When the reduction is carried out in the absence of a proton donor, the major products arise from dimerization (e.g., of 218, Table 18)[‌467‌] and from polymerization of the radical anion intermediates.[‌468‌] Today, anionic polymerization is generally initiated with alkyllithium reagents. Allylic urea 219 undergoes chemoselective reduction of the styrene double bond in the presence of the indole moiety. Reductive cleavage of the allylic urethane produces the major side product, which can be suppressed by using a proton source whose conjugate base is sufficient to deprotonate the urethane and protect it from subsequent reductive cleavage.[‌469‌]

Meeee 88 Meeeeeeeee Meeee Meeeeeeeee ee Meeeeeee[‌888‌,‌888‌,‌888‌‌888‌]

Meeeeeeee Meeeeeeeee Meeeeee(e) Meeee (%) Mee
Me, MMM, MeMM (8 eeeee) e,e [‌888‌]
Me, eee MM8, MeMM8, MMM, 88°M 88 [‌888‌]
Me, MM8, Me8M 88 [‌888‌]
Me, MM8, e-MeMM, MMM, 88°M 88 [‌888‌]
8. Me, MM8, MMM, 88°M, 8eee8. MM8Me 88 [‌888‌]
Me (8 eeeee), MM8, MMM, MeMM 88 [‌888‌]

e Mee eeeeeeee; 8:8 eeeee ee eeeeeeee.

e Meeeeeeeeee eeeeeeeeee: Me, MMM, MeMM (8 eeeee); eeeee: 8%+88%.

Meeeeee ee eeeeeeeeeeeeeeee ee eeeee e eeeeeee ee eeeeeeeeee eeeee eeeeeeeeee. Meeeeeeee ee 888 eeeeeee ee eeeeeeeee ee eee eeeee eeeeeee eeee ee eeeeeeeeeeee eeeeeeeee, eeeeeeeee eee eeeeeeee eeeeeee ee eee eeeee.[‌888‌] Mee eeeee eeeee, eeeeeee eeeeee eeee, eee eee eeeeeeeee eeee eee eee eeeeeee ee 888 ee eeee eee eeeeeee ee eeeeeeeee eeeeeee eeeee.[‌888‌] Meeeee-eeeeeeeeeee eeeeeee eee eeee eeeeee eeeeeee[‌888‌] eee eeeeeeeee ee 888 eeeeeee eee eeeeeeeeeee-eeeeeeeeeee eeeeeee ee eeeeeeeee eeeee.[‌888‌] Meeeeeeeee eeeeeee, Meeee, eee MM eeee eeeeeeeeee ee 888 eeeee ee eeeeeeeee eeeeeee eeeee ee eeeeee 888 eeee eeeeee Me ee eeeeeeee (eee Meeeeee[‌888‌] Meeeeeeee 8 eeeeeeeeeee ee eeeeeee, eeeeeeeeeeee eeeeeeee eee ee eeeeeeee ee eeeeee eeeeeeee, eeeeeeeeeeee eee eeeeeeee eeeeeeeeee ee eeee eeeeeeeeeeeee (e.e., eeeeeee eeeeee eeee > eeeeeeee eeeeeee > eeeeeeeeeeeeee eeeeeeeee eeee ee eeeeeeeeee). Mee MM eeee ee eeeeee-eeeeeeeeeee eeeeeeeeeeeee ee eeee eeeeeee eeeeeee.[‌888‌,‌888‌]

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

Meeee 88 Meeeeeeeee Meeee Meeeeeeeee ee Meeeee[‌888‌‌888‌,‌888‌]

Meeeeeeee Meeeeeeeee Meeeeee(e) Meeee (%) Mee
Me, MMMe 88 (88:8) [‌888‌]
Me, MMMe 88 (8:88)
Me, Me8Me 88 (88:88)
Me, eeeeeeeeeee, MMMe 88 (88:88)
8. Me, MM8, Me8M
8. MeMM, Me8M
88 [‌888‌]
8. MeMe ee MM (8.8 eeeee)
8. Me, MMMM, 8,8,8,8-eeeeeeeeeeeeeeeeeeeee, 88eee ee 8e
8. Meeeeeeeee eeee MM8Me, eeeeeee eeee MM8Me8
88e [‌888‌]
8. Me (8 eeeee), MM8, MMM
8. MeMM8Me
88 [‌888‌]

e Meeeeeee eeeeeeee ee eeeee.

e Meeeeee eeeeeeee.

e 88% ee eee Δ8,8-eeeeee eee eeee eeeeeeee.

Me eeeeeeeeee eeeeee 8-eeeeee-8,8-eeeeee eeee eeeeee eeeeeee ee eeeeeeeeeeeee eeeeeeee.[‌888‌] Meeeeeeeeeeeeeeee eee eeeee eeeeee eeeeeee eee ee eeeeeee eeee eeeeeee ee eeeeee eeeeee eeeeeeeee eeeeeeeeeee[‌888‌] e eeeeeee eeeee ee eeeeeeeeeee ee eeeee eeeeeeeeeeee.[‌888‌,‌888‌] Meeeeeeee eeeeeeeeee ee M88 (eeeeeee, eeeeeeeeeeeeeeeeeeeeee, eeee-eeeee eeeeeeeee eeeeeee) eeeeeee e M88 eeeee eeeeee ee e eeeeeeeeeeeeeeeee eeee, ee eee eeeee.[‌888‌] Meeeeeee eeeeee eeeee ee eeeeee eeeeeee (e.e., eeeee-eeeeeeeeeee [8]eeeeeeeee) eeee eeee eeeeee eeeeeeeeee eeee eeeeeeeee eeee eeeeeee eeeee.[‌888‌,‌888‌] Meeeeeee eeeeeeee eeeeee eeeee eee eeeeeeeee eeeeeeeee ee Meeee eeeeeeeee (e.e., eeeeeeeeeeeeee, eeeeeee), eeee eee ee eeeeeee eeee eeeee ee eeeeeeeee ππ eeeeeee eeeeeee (e.e., eeeeeeeeeeeee)[‌888‌] ee eee eeeeeeee eeeeeeee eeeeee ee eeeeeeeeeeeeeeeee[‌8‌,‌888‌,‌888‌,‌888‌] ee eeeeeeee. Mee eeeeeeeee eeeeeeeeee (e.e., eeee eeeeeeeeeeeee) eeeeeee eee eeeeeeee eeeeeee ee: eeeeeeeeeee > 8-eeeeeeeeeeeeeeeee > 8-eeeeeeeeeeeeeeeee (eeeeeeee eeeee=88:88:8, eeeeeeeeeeee), eeee eeeeeeeeee (888) > eeeeeeeeeeee (8) > eeeeeeeeeeee > eeeeeeeeeee > eeeeeeeeeee (8) eeeee ee eeeeeeee eeeeeeeeee.[‌8‌,‌888‌,‌888‌]

Meeeeeeeee eeeee eeeeeeeee ee eeeeeeeeeeeee eeeeeee[‌8‌,‌888‌,‌888‌] ee e eeeeeeeeeeee eeeeeeeee eeeeee eee eee eeeeeeeeeeeeeee eeeeeeeeeee ee eeeeeee (Meeee 88). Meeeeeee eeeeeee eee eeeeeeeeeeee ee eeeeeeeeeeeeee eee eeeeeeeee eeee eeeeeeeee. Meeeee-eeeeeeeeeee eeeeeee[‌888‌,‌888‌] eee eeeeeeeeeeee[‌888‌,‌888‌] eeeeeeeee eeeeee M-eeeeeee, eeeee eeeeeee eeeeeee eeeeee M-eeeeeee. Meeeeeeee eeeeee eeeeeeeeeeee ee eeeeee eeeeeee eeeeeeeeeeeeeee[‌888‌,‌888‌] eeeee eeeeeeeee ee eeeeeeeeee eeeeeeeee. Meeee eeeeeeee eeee eeee eee-eeeeeeeee ee eeee eeeeee eeee eeeeeee eeeeeeee.[‌888‌] Meeeeee eeeeee eee eeeeee-eeeeeeeeeee eeeeeeeeeeeeee eeeeeeee eee eeeeeeeeee ee eeeeeeee (eeeeeee eeeee, eeeeeeeeeeeeeee) eeeee eeeeeeeee eeeeeee eeeeeee eeeeeeeeeeeeee eeeeeeee eee eeeeeeeeeeeee eeee eeeeee. (M)-8,8-Meeeeeeeeee-8-eee, eee eeeeeee, eee e eeee-eeee ee eeeeeeeeeeeee 888 eeeee ee eeeeeee eeeee eeeeeeee ee 888 eeeee eee eeeeeeeeeeee eeeee eee eeee eeeeeeeeee.[‌888‌] Meeeeeeee ee eeeeeeeeeeeeeeeee (888) eeee eeeeeee ee eeeeeeeeeeeeeee ee eee eeeeeeeeeee eeeeeee e eeeeeeeeeeee eeeee ee eee-eeeeeeee, eeeee eeeeeeeee eeee eeeeee eeeeeee eeeee-eeeeeeee.[‌888‌‌888‌] Meee eeeeee eeeeeee eeeeeee ee eee eeeeeeeee ee e eee-eeeeeee M-eeeeeeeeeeeeeeee eeeeeeeeeee ee eee eeeeeeeeeee eeeeeeee eeeeeeee ee eeeee eee M-eeeeeeeeeeee ee eeee eeeeee.[‌888‌] Meeeeeeee ee eeeeeeeeeee[‌888‌] eeee eeeeee ee eeeeee eeeeeee ee eeeeeee ee eeeeeee eeeee[‌888‌] eeeee eeeeeeeeeeeee eee eee-eeeeee, eeeee eeeeeeeee eeee eeeeeeeeeeeeee eeeee eee eeeee-eeeeee ee e eeeeee eeeeeeeeeeeeeee eeeeeee. Meeeeeeeeeeee eeeee eee eeeee-eeeeee eee eee ee eee eeeeeeee eeeeeeeeee. Meeeeeeee eeee eeeeeee ee eeeeeeeeeeeee eeeeee eeee eeeeeeeee eeee eeeeee.[‌888‌] Meeeeeeee ee eee-eeeeeeeeeee eee eeee eeeeeeeeeeee ee eeeeeeeee ee eeeeeeeee-8,8-eeeee (eee eeeeeeeeeeeee ee eeeeeeeeeee eeee eeeeee eeeee > eeeeeee eeeee).[‌888‌] Meeeeeeee ee eeeeeeeee eeee eeee eeeeeeeeeeeeee eeeee ee eeeeeee ee eeeeeeeeeee eeeeeeee eee eeeeeee e eeeeee eeeeeeeeeeee eeeee ee eeeeeee eeee eeeeeeeee ee ee eeeeeeeee ee eeee eeeeeeeeeee (e.e., 888).[‌888‌] Me ω-eeeeeeeeeeeeeee eeee eeeeeee e eeeeeee ee eeeeeeee eeeeeee eeee eeeeeeeee eeeeeeee ee eee eeeeee eee MM eeee eeeeeeee eeeee eeeee eeeeeeeeee.[‌888‌] Mee eeeeeee eeeeeee ee ee eee ee eeeeee eeeeeeeeee eee eeee-eeeee eeeeeeeeee eee eeeeeeeeeeee eeee eeeeeeee e eeeee eeeeee ee eeee-eeeee eeeeeee ee eeee eeeeeee eee eeeeee eeeeee (eeeee eeee eeeeeeee eeeeeee ee eeeeeeeeee eee eeeeeee eeee-eeeeeeee)[‌888‌] ee eeeeeee-8,8-eeeeeee[‌888‌] ee eeeeeeee eee eeeeeeeeee ee eeee-eeeee eeeeeee. Meeeeee ee eeeeeeee ee eeeeee eeeeeee ee eee eeeeee eeee ee eeeeeeee eeee eeee-eeeee eeeeeee eee eee eeee eeeeeeee ee eeeeeee eeeee, eeeee eeeeeeeee eee eeeeeeeeeeeee ee 8,8-eeeeee ee eee eeee eeeeee eeeeeee 8,8-eeeeee. Meeeeee eeeee ee eeeeeee, ee eeeeeeeeeeeeeeeeeeeeee, eee eeeeeee eeeeee ee eee eeeeeeee ee eeee-eeeee eeeeeee eeeeeeeeee eee eeeeeee eeeeee eeeeeeeeeeeee eeeeeeee (e.e., 888) ee eeeee eeeeeeeeeee eeeeeeee (e.e., 888) eeee eeeeeeeee eeeeeeeeeeeeeeeee eee eeeeeeee eeeee. Meeeeee ee eee eeeeeeee ee eeeeee ee eeeee eeeeeeeeee ee eeeee ee eeeeeeeeeeeeeeeee, eeee ee eeeeeeeee, eee eee eeeeeee ee eeeeeeeeeeeeee. Mee eeeeeeeeeeeeeeeeeee eee eeeeeeeeee ee eeeeeee eeeeeeee eeeeeee eeeeeeeeee eeeee eee eeeeeeeee ee 88888°M.[‌888‌] Mee eeeeeeeee eeeeeee ee eeeeeee eeeeeeeeee ee eeeeee eeeeeeeeeee ee eee eeeeeeeeeeee eeeeeeeeeeeeeee eeeeeeeee ee e eeeeeeeee eeeeeee eee eeeeeeeeeeee ee ee 8-eeeeee-8,8-eeeeeeeeee-8-eee (e.e., 888) eeeee Meeeeeee eeeeeeeeee.[‌888‌] Meeeeeeee eeeeeeeee ee ee eeeeee eee eeeee ee eee eeeeeeee ee eeeeeeee eeeeeeeeeeeee eeeeee ee eeeeeeeee ee eeeeeeeee ee eeeeeeeeee (e.e., eeeeeeeeee eeee eeeeee ee 888).[‌888‌]

Meeee 88 Meeeeeeeee Meeee Meeeeeeeee ee Meeeeee[‌888‌,‌888‌,‌888‌‌888‌]

Meeeeeeee Meeeeeeeee Meeeeee(e) Meeee (%) Mee
8. Me, MMM, 88°M
8. MeMM, 88°M
888 [‌888‌]
Me, eee MM8, MMM, eeeeeeeee, ee, 88e 88 [‌888‌]
Me, MM8 88 [‌888‌]
Me, MM8, MMM 88 [‌888‌]
Me, MM8, Me8M 88 [‌888‌]
Me eeeeee, Me8M, e-MeMM 88 [‌888‌]
Me, MeMM8, e-MeMM 88 [‌888‌]
Me, MeMM >88 [‌888‌]

Meeeeeeeeeee Meeeeeeee

8β,8ε,8ε,88ε,88ε-8-Meeeeee-8,8-eeeeeeeeeee-88-eee; 888:[‌888‌]

Me e eeee ee Me (88ee, 8.88eeee) ee MM8 (88eM) eee eeeee 888 (88ee, 8.88eeee) ee Me8M (8eM). Meeee 8e, MeMM/Me8M (8:8, 8eM) eee eeeee eee eee MM8 eeeeeee ee eeeeeeeee. Meeeeeee ee M8M eee Me8M eeeeeeee ee eeeeeeeeee eeeeeeee eeeeeeeeee ee eee eeeeee. Mee Me8M eeeee eee eeeee (Me8MM8) eee eeeeeeeeeeee. Meeeeeeeeeeeee (eeeeee eee, eeeeee/Me8M 88:8) eeee eee eeeeeee; eeeee: 88ee (88%).

(M)-Meeeeeee-8-ee-8-ee (888):[‌888‌]

MM8 (888eM) eee eeeeeeeee eeee e eeee ee eeeeeeeeeeee eee eeeeeeeeeeee eeee e eeeee eeeeee ee e eeee (88°M) Meeee eeeeeeeee. Meee e eeeeeeeee eee eeee, eee eeeeeeeeeee eeeeee eee eeeee eeeeeeee ee eeeee eeeee ee eee eeeee eeeee eee eeee eeeee eeeeeeeee. Mee Me eeeee (888ee, 88.8eeee) eee eeeee eee eee eeeeeee eee eeeeeee eee 8.8e. Meeeee 888 (8.88e, 88eeee), eeeeeee eeee Me8M (eeeeeee eM), eee eeeee eeeeeee eee eee eeeeeee eeeeeee eee 88e (88e eeee MMM eee eeee ee e eeeeeeeee). Mee eeeeeeee eee eeeeee ee ee eeeeeeeeeee ee eee eeeeee Me eeeee eeee MeMM8Me, eeeeeeeeeee ee eee MM8, eeeeeeee eeee M8M, eee eeeeeeeeee eeee Me8M ee eeee eee eeeeeee; eeeee: 8.88e (88%).