Science of Synthesis

Jammi, S.; Nottingham, C.; Guiry, P. J., Science of Synthesis: Metal-Catalyzed Cyclization Reactions, (2016) 1, 55.

General Introduction

The vinylation of aryl/vinyl/alkyl halides or pseudohalides catalyzed by palladium(0), the Heck cross-coupling reaction, has developed into one of the most widely employed C—C bond-forming reactions in organic synthesis since its discovery in 1968 by Heck.[‌1‌–‌3‌] The intramolecular version of this reaction was first realized by Mori and co-workers in 1977 through the formation of indole ‌1‌ (‌Scheme 1‌).[‌4‌] Since then the intramolecular Heck reaction has been extensively utilized in the construction of isolated, fused, bridged, or spiro rings of various sizes and as a key step in the total synthesis of many natural products.[‌5‌] Its application in cascade/domino processes has further increased the usefulness of the reaction in multiple bond formation to construct cyclic or polycyclic systems in both asymmetric and nonasymmetric modes. Additionally, tertiary or quaternary stereocenters can be established using the asymmetric intramolecular Heck reaction.[‌6‌–‌8‌]

‌Meeeee 8‌ Meeeeeeeeeeeee Meee Meeeeeee Me Meee ee Meeeee[‌8‌]

Mee eeeeeeee eeeeeeee eeeeeeeee eeeee eee eee eeeeeeeeeeeeee Meee eeeeeeee ee eeeeeeee ee eeeeeee eeee eeeee eeeee (‌Meeeee 8‌). Mee eeeee eeee ee eee eeeeeeeee eeeeeeee ee ee eeee/eeeee/eeeee eeeeee ee eeeeeeeeeeee ee e eeeeeeeee(8) eeeeeee ‌8‌ ee eeee e eeeeeeeee(MM) eeeeeee ‌8‌. Me eee eeeeee eeee, eeeeeeeeeeee ee eeee eeeeeeeee(MM) eeeeeee, eeeeeeee ee eeeeeeeeeeee ee e eeeeeeee eeeeee, eeeee ee eee eeeeeeeee ee e π-eeeeeee ‌8‌ ee ‌8‌. Meeeeeeee ee eee eeeeeeee eeeeeeeeee, eee eeeeeeeee eeeeeeee eee eeeeeeeeeeee ee eeeeee e eeeeee (eeeeeeee eeeee) ee eee ee eee eeeeeee eeee eee eeeeeeeee(MM) eeeeeee ‌8‌ (eeeeeee eeeee) ee eeeee eee eeeeeeeeeeee ee eee eeeeee. Me eee eeeee eeee, eee-eeeeeeeee ee eee eeeeee eeee eee Me—M eeee ee eee π-eeeeeee eeeeee, eeeeeeeee σ-eeeee eeeeeeeee(MM) eeeeeeeee ‌8‌/‌8‌ ee ‌8‌/‌8‌. Me eee eeeeee eeee, eee-β-eeeeeeee eeeeeeeeeee eeeee eeee ee eee Meee eeeeeeee eee eee eeeeeeeeeeeeeeee eeeeeee ‌88‌ ee ‌88‌. Me eee eeee eeee, eeeeeeeeeeeee eeeeee eeeeeeeee(8) eeeeeee ‌8‌ ee eeeeeeeeeee eeee eee eeeeeeeeeeeeeeee eeeeeee ‌88‌ ee ‌88‌ ee eeee-eeeeeeee eeeeeeeee eeeeeeeeeee ee eeeeeeee eee eeeeeeeee eeeee.

‌Meeeee 8‌ Meeeeeeee Meeee eee eee Meeeeeeeeeeeee Meee Meeeeeee

Me eeee eeeeeee eee eeee eeeeeee eee eee eeeeeeeeeeee ee eeeeee eeeeeee eeeee eeeeeeeeeeeeee Meee eeeeeeeeeeee, eeeeeeeee eeeeeeeeeeeeeeee eeeeeeee, eee eeeeeeeee. Mee eeeeeeee eeeeeeeee eeeeee eee eeeeeeeeeee eeeeeeeee ee Meeeeeeʼe eeeee.[‌8‌] Meeee eeeeeeeeee eeeeeeeeee eee eeeeeeee ee eee eeee ee eee eeee eeeeee, eee eeeeee ee eeeeeeeeeee (eeee eee eee eee eeeeee eeee eeeeeeee ee eee eeeeee eeeeeeeee ee eeee eee ee eeeeeeee eeeeee), eee eee eeeeeeee ee eee eeeeee eeeeeeeeee eeeeeeeeeee (e.e., eeee eee e eeeeeeee/ee8 eeeeee).

References