A Highly Stereoselective Sequential Allylic Transfer Reaction of Diene with Diboronyl Reagent and Aldehydes Promoted by Nickel Catalyst

Abstract

[reaction: see text] A new protocol for the sequential allylic transfer reaction of a diene with two aldehydes in the construction of cyclic systems containing four stereogenic centers is achieved in a one-pot operation. Reaction of the diene-alehyde 1 with aldehyde in the presence of the diboronyl reagent catalyzed by a nickel complex produces products 2 and 3 depending on reaction conditions in high levels of diastereoselectivity. Extension of this method to the synthesis of six-membered rings is also investigated.

Catalytic bismetallative multicomponent coupling reactions: scope, applications, and mechanisms

“…coupling of an aldehyde, a diene, and a diboron reagent followed by allylboration with another aldehyde) as shown in Scheme 29. 35, 36 The reaction of a diene-aldehyde 104 , benzaldehyde ( 78 ), and a diboron reagent 105 at 20 °C in the presence of Ni(cod) 2 and P(2-furyl) 3 afforded 106 in 87% yield. The unexpected stereochemical inversion of the product was observed at different reaction temperatures; when the subsequent allylation with benzaldehyde ( 78 ) was carried out at −78 °C (instead of at 20 °C), compound 107 was obtained as a single isomer.…”

“…coupling of an aldehyde, a diene, and a diboron reagent followed by allylboration with another aldehyde) as shown in Scheme 29. 35,36 The reaction of a diene-aldehyde 104, The unexpected stereochemical inversion of the product was observed at different reaction temperatures; when the subsequent allylation with benzaldehyde (78) was carried out at À78 1C (instead of at 20 1C), compound 107 was obtained as a single isomer. Additionally, a six-membered ring moiety (109) can be also prepared by this process from a diene-aldehyde 108, benzaldehyde (78), and 105 in the presence of a nickel catalyst (74% yield).…”

Transition metals in organic synthesis: Highlights for the year 2005

“…Nickel catalyzed the cyclization of 5,7-and 6,8-dienals with an aldehyde, and a diboryl reagent (Eq. (300)) [1394]. Nickel catalyzed a diastereoselective cyclization of chiral alkenyl sulfoxides having a tethered alkenyl ester (Eq.…”

Synthetic Approaches to Spiro-oxindoles and Iminoindolines Based on Formation of C2–C3 Bond

“…This reaction was extended to include the formation of two carbon-carbon bonds by sequential allylic transfer reactions in one pot by Yu. 35 The nickel-catalyzed cyclization of 1,3-dienes with internal and external aldehydes in the presence of a diboronyl reagent proceeded in high levels of diastereoselectivity. Based on this bismetallative cyclization process, we (Table 4).…”