Nickel‐Catalyzed Allylmethylation of Alkynes with Allylic Alcohols and AlMe₃: Facile Access to Skipped Dienes and Trienes

Abstract

We present herein an unprecedented allylative dicarbofunctionalization of alkynes with allylic alcohols. This simple catalytic procedure utilizes commercially available Ni(COD)2, triphenylphosphine, and inexpensive reagents, and delivers valuable skipped dienes and trienes with an all‐carbon tetrasubstituted alkene unit in a highly stereoselective fashion. Preliminary mechanistic studies support the reaction pathway of allylnickelation followed by transmetalation in this dicarbofunctionalization of alkynes.

Silaborative Assembly of Allenamides and Alkynes: Highly Regio‐ and Stereocontrolled Access to Bi‐ or Trimetallic Skipped Dienes

“…[7] As multi-substituted skipped 1,4-dienes are ubiquitous in natural products [8] and have high synthetic potential, [9] a modular atom-and step-economical synthetic approach to these compounds would have a significant impact. Numerous synthetic methods such as hydroallylation of alkynes, [10] hydroalkenylation of 1,3-dienes, [11] and coupling of vinyl metallic reagents with different allylic electrophiles [12] have reached impressive levels of sophistication, and are powerful strategies for preparing skipped 1,4-dienes. However, the incorporation of metallic reagents in these processes to facilitate further functionalization is rare (Scheme 1A).…”

Silaborative Assembly of Allenamides and Alkynes: Highly Regio‐ and Stereocontrolled Access to Bi‐ or Trimetallic Skipped Dienes

“…[7] As multi-substituted skipped 1,4-dienes are ubiquitous in natural products [8] and have high synthetic potential, [9] a modular atom-and step-economical synthetic approach to these compounds would have a significant impact. Numerous synthetic methods such as hydroallylation of alkynes, [10] hydroalkenylation of 1,3-dienes, [11] and coupling of vinyl metallic reagents with different allylic electrophiles [12] have reached impressive levels of sophistication, and are powerful strategies for preparing skipped 1,4-dienes. However, the incorporation of metallic reagents in these processes to facilitate further functionalization is rare (Scheme 1A).…”