ABSTRACT
The present paper reports a remote carbon-to-carbon boryl migration via an intramolecular 1,4-B/Cu shift, which establishes an in situ stereospecific electrophilic trap on the alkene moiety. The synthetic application is developed to prepare functionalized cyclopentenes by means of a palladium-catalyzed regioselective intramolecular coupling that completes a strategic cyclopropanation and generates valuable structural bicyclic systems. The mechanism is characterized by DFT (density functional theory) calculations which showed that the 1,4-migration proceeds through an intramolecular, nucleophilic attack of the copper-alkyl moiety on the boron atom bonded to the C(sp2), leading to a 5-membered boracycle structure. The computation of the 1,3- and 1,4-B/Cu shifts is also compared as is the impact of the endo- or exocyclic alkene on the reaction kinetics.
ABSTRACT
Regioselective borylcupration of borylated skipped (Z)-dienes generates diborylated alkylcopper species that are involved in an intramolecular stereospecific B/Cu 1,3-rearrangement by migration of Bpin moiety from C(sp2 ) to C(sp3 ). DFT mechanistic studies showed that boryl migration occurs through the formation of 4-membered boracycle intermediate with a moderate free-energy barrier. Moreover, the use of KOMe forms stable Lewis base adducts with Bpin moieties that blocks the reaction. Subsequently to the 1,3-boron shift, the in situ electrophilic trapping allows selective C-H, C-C and C-X bonds, followed by intramolecular cross coupling giving access to cyclic functionalized alkylidenecyclohexanes or alkylidenecyclobutanes.
ABSTRACT
Palladium catalyzes the cyclopropanation of 2-substituted 1,1-diborylalkenes with (trimethylsilyl)diazomethane. The relative stereoselectivity is controlled via a carbene insertion sequence generating an exclusive anti conformation between the R and SiMe3 substituents. Mixed 1,1-diborylalkenes also contributed to the formation of stereoselective B, B, Si-cyclopropanes. Orthogonal activation with NaOtBu gives protodeborylation preferentially on the boron moiety syn to the aryl group. Further oxidation gives access to polyfunctional cyclopropyl alcohols with controlled enantioselectivity when chiral boryl motifs are involved.
ABSTRACT
Exchange of boryl moieties between alkenylboranes and diboron reagents has been postulated as a stereospecific cross-metathesis pathway with concomitant formation of mixed diboron reagents. DFT calculations propose a mechanism for the stereocontrolled C(sp2)-B/B'-B' cross-metathesis with both symmetric and non-symmetric diboron reagents.
