Science of Synthesis

Nahra, F.; Riant, O., Science of Synthesis Knowledge Updates, (2013) 2, 202.

The addition of silyl nucleophiles to α,β-unsaturated carbonyl compounds is by far the most used approach to form the β-silyl carbonyl system. In recent years, development of this method has exploded onto the scientific scene due to the now widely used Suginome reagent ‌19‌ (‌Scheme 8‌). Transition-metal catalysts are especially efficient in this type of reaction, giving access to high yields of the desired products with good selectivity. The rhodium-catalyzed conjugate addition to cyclic Michael acceptors ‌18‌ followed by protonation provides the β-silyl ketone or lactone products ‌20‌.[‌55‌,‌56‌] A rhodium(I) perchlorate catalyst {[Rh(cod)(dppp)]+ClO4–} is used and additional ligand is necessary to give satisfactory yields.[‌55‌,‌56‌]

‌Meeeee 8‌ Meeeeeeee Meeee Meeeeeee eeee Meeeee Meeeeeeee[‌88‌,‌88‌]

‌Meeeeeeeeee 8‌

Meeeee-eeeeeeeee eeeeeeeeeeee ee eeeeeeee eeeeeeeeeeeeeeeeeee (‌88‌) eeee eeeeeeeeeeee eeeeeeeee 8,8,8,8-eeeeeeeeeee-8,8-eeeeeeeeeeeeeeee (‌88‌) ee ee eeee eee eeeeeeeeeeeeeee eee ee eee ee e β-eeeee eeeeeeee eeeeee eeeeeeee β-eeeee eeeeeeee ‌8‌ eeeee eeee eeeeeeeee (‌Meeeee 8‌).[‌88‌] Meee eeee ee eeeeee eeeeeeeee eee eeee eee eeeeeee ee eeee eeeeee eeeeeeeeeeee, eeeeeeeeee eeeee eee Meeeeeee eeeeeee ‌88‌. Meeeee eee eeeeeeee ee eeee eeeeeeee eeee ee eeeeeee eeeeeeeee eeeeeeeee eee eeeeee.[‌88‌] Móeeeee[‌88‌] eee Meeeeee[‌88‌] eeee eeeeeeeeeeeee eeeeeeeee eeeeee-eeeeeeeee eeeeeeeeeeeeeeee eeeeeeeee eeeee eeeeeeeee, eeeee eeeeee e eeeeee eeeeee eeeeeeee ee e eeeeee eeeee ee eeeeee M-eeeeeeeeeeee eeeeeee–eeeeee eeeeeeeee, eeeeeeeeeeee.

‌Meeeee 8‌ Meeeee-Meeeeeeee Meeeeeeeeeee ee ee Meeeeeeeeeeeeeeeee[‌88‌]

Meeeeeeeeeeeeeee eeeeeeeeeeeeeee eee eeee eeee eeeeeee, eee eeee eeeee eeeeee eeeeeeeeeeee, eee eeeeeee eeee eeeeeee ee eeee eeeeeeeeeeeeeeee eeeeeeeee eeeee eeeeeeee ee eeeee eeeeeee eeeeeeee. Mee eeeeeeeeeeee eeeee ‌88‌ eee ee eeeee ee eeeee (M)-8-eeeeeeeeeeeeee (‌88‌) ee eee eeeeeeee ee e eeeeeee eeeeeeee eee (M)-8,8′-eee(eeeeeeeeeeeeeeeee)-8,8′-eeeeeeeeee [(M)-MMMMM] ee eeeeeeeeeee eeeeee eee eeeeeeeeee ee eee β-eeeeeeeeeee eeeee eeeeeeee eeeeeee ‌88‌ (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeeeeeeeeee Meeeeeeee Meeee Meeeeeee eeee ee Meeeeee Meeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

8-[Meeeeeee(eeeeee)eeeee]eeeeeeeeeeeeee (‌88‌, M = MM8; e = 8); Meeeeee Meeeeeeee:[‌88‌,‌88‌]

M Meeeeee eeee eeeeeeee eeee e eeeeeeee eeeeeee eee eeeee ee eeeee eeeeeeeeee eee eeeeeee eeee [Me(eee)(eeee)]+MeM8– (8.8 eee%) eee eeee (8.8 eee%). Meeee eeeeeeeee eeee eeee eeeeeeeee ee eeeeeeeeeeee 8,8-eeeeeee/M8M (88:8; ee. 8.8 M eeeee ee eeeeeeeee). Meeeeeeee-8-eeeee (8.8 eeeee), eee eeeeeeeeeeee eeeee ‌88‌ (8.8 eeeee), eee Me8M (8.8 eeeee) eeee eeee eeeee eee eee eeeeeee eee eeeeeeeeee ee 88 °M eee 88 e. Meeee eeeeeee ee eee eeeeeee ee ee, eeeeee eee eee eeeee eee eee eeeeeeee eeee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeeeee/MeMMe); eeeee: 88%.

Meeeeeee 8-{[Meeeeeee(eeeeee)eeeee](eeeeee)eeeeee}eeeeeeee (‌8‌); Meeeeee Meeeeeeee:[‌88‌]

(MeMMe)8•eeeeeee (8.8 ee, 8.8888 eeee, 8.8 eee%) eee eeeeeeee eeeeeeeeeeeeeeeeeee (‌88‌; 8.8 eeee) eeee eeeee ee e eeeee-eee eeee eeee ee e M8-eeeeee eeeeee. Mee eeee eeee eee eeeee eee ee eee eeeeee eee eeeeee eeeee e eeeeeeee eeeeeeee ee M8. Meeeeee (8.8 eM) eee eeeeeeee (88 eee%) eeee eeeeeeeeeeee eeeee ee eee eeee eee eeeeeee. Meeeeee, 8,8,8,8-eeeeeeeeeee-8,8-eeeeeeeeeeeeeeee (‌88‌; 8.88 eeee) ee MMM (8.8 eM) eee eeeee eee eeeeeee. Mee eeeeeee eee eeeeeee eee eeeeee ee 888 °M ee ee eee eeee eeeee M8 eee 88 e, eee eeee eeeeeee ee eeee ee ee. M8M (8–8 eeeee) eee MeMM•M8M (eeeeeee eee) eeee eeeee, eee eee eeeeeee eee eeeeeee eee 88 eee. Mee eeeeeee eee eeeeeeeeeee eeeeeee M8M (8 eM) eee Me8M (8 eM), eeeeeeeee, eee eee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8 × 8 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee M8M (8 ×) eee eeee eeee eeeee, eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeeeee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeee 8:8) ee eeee e eeeeeeeee eee; eeeee: 88%.

Meeee (M)-8-[Meeeeeee(eeeeee)eeeee]-8-eeeeeeeeeeeeeeee (‌88‌); Meeeeee Meeeeeeee:[‌88‌]

[Me(eee)8]MMe (8.8 eee%) eee (M)-MMMMM (88 eee%) eeee eeeeeeeee ee 8,8-eeeeeee/M8M (88:8; 8.8 eM) ee e eeeee-eeeee Meeeeee eeee eeeeeeee eeee e eeeeeeee eeeeeee eee, eee eee eeeeeee eee eeeeeee eee 88 eee. Meeeeeee ‌88‌ (8.8 eeee), Me8M (8.8 eeee, 8.8 eeeee), eee eee eeeeeeeeeeee eeeee ‌88‌ (8.8 eeee, 8.8 eeeee) eeee eeeee ee eeee eeeee. Mee eeeeeee eee eeeeeee ee 88 °M eeeee MMM eeeeee eeeeee eeeeeeee eeeeeeeeee ee eee eeeeeeeee. Meeee eeeeeeeee ee eee eeeeeeee eeee MeMMe, eee eeeeeeee eeee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeeeee/MeMMe 88:8); eeeee: 88%; >88% ee. Me eee eeeeeee eee eeeeeeeeeeee eeee eee eeeeeee eeeeeeee, eeeeeee eeeeeeeeeeee eee eeeeeeee ee eeeeeeeeeee ee eee eeeee-eeeeeee eeeeeeeee eeeee eeee eeeeee ee eeeeeeee eeeeeeee eeeeeeeeeeee.

References