Catalytic intermolecular allyl–allyl cross-couplings between alcohols and boronates

Abstract

We developed catalytic intermolecular C(sp(3))-C(sp(3)) cross-couplings between various allyl alcohols and allyl boronates, which proceeded smoothly in the presence of nickel(0) under mild conditions to form 1,5-dienes with excellent linear- and γ-selectivity; the use of boronates proved to be crucial in terms of reactivity.

Nickel‐Catalyzed Direct Coupling of Allylic Alcohols with Organoboron Reagents

“…The results indicated that the Lewis acidic features of organoboronic acid derivatives are required for this reaction. Allylic alcohol may be activated by the coordination with arylboron compounds [9] or forming a boronate [14] to facilitate the oxidative addition step. It should be noted that the coupling methods that could accommodate both organoboronic acid and other boron regents are quite rare.…”

“…In 2011, Kobayashi and coworkers developed a nickel-catalyzed allyl-allyl cross-couplings between alcohols and allyl boronates. [9] However, no allyl-aryl crosscoupling via reactions with arylboron reagents was described in this paper. In addition, Ni(cod) 2 was ineffective for this reaction.…”

“…During our work on nickelcatalyzed coupling reactions, [11] we found a new nickel-catalyzed direct coupling of allylic alcohols with arylboronic acids. Com-pared to known methods, [5][6][7]9,10] this reaction has some advantages such as avoiding the use of any ligands or activators, [12] and milder reaction conditions (50 o C in most cases). The method was also successfully extended to arylboronic esters, boroxines or triarylborons.…”

CaII‐Catalyzed Alkenylation of Alcohols with Vinylboronic Acids

“…Leboeuf 4 ,e ntry 15). [12] Finally,t he reaction was attempted with (E)-styrylsilane 2e,asubstrate that has already been used by Niggemann et al for af ew calcium-catalyzed alkenylation of alcohols.…”

Ni- and Pd-Catalyzed Synthesis of Substituted and Functionalized Allylic Boronates

“…More recently, allylic boronates have been used as partners for cross-coupling reactions with aryl 6 and allyl electrophiles. 7 Due to the importance of allylboronate building blocks in synthetic organic chemistry, their synthesis has been the subject of many studies. Besides stoichiometric substitution reactions that involve allyllithium 8 or allylmagnesium 9 reagents, homologation of vinyl boronates 10 has also been a practical route to many of these materials.…”