Addition of Metal Enolate Derivatives to Unactivated Carbon−Carbon Multiple Bonds

Copper-Catalyzed Electrophilic Amination of sp2 and sp3 C−H Bonds

“…[125][126][146][147][148][149][150][151][152][153][154][155][156][157][158][159][160][161][162] In comparison to commonly used carbonyl αalkali and alkaline-earth enolates, they offer an ideal combination of good reactivity and tolerance toward many functional groups. [125][126][146][147][148] So far, zinc enolates have been successfully applied toward carbon-carbon bond formation with aldol additions to carbonyls, [157][158] nucleophilic additions to alkenes, [159][160] as well as a variety of transmetallation reactions such as α-arylation [125][126][149][150][151][152][153][154][155][156] and α-allylation. [161][162] However, the potential of zinc enolates remains underexplored for the synthesis of α-heteroatom substituted carbonyl molecules, such as α-amino carboxyl derivatives, one of the most biologically important carbonyl compounds.…”

Carbon–Carbon Bond Forming Reactions Mediated by Organozinc Reagents

“…Similarly, the Ti(II)-catalyzed hydrozincation reaction of dienes [95] and alkynes [96] has been reported, but is limited in the latter to di-substituted alkynes and shows a moderate regioselectivity. The carbozincation reaction of alkenes [97] has so far been mainly used in the case of ethyl group incorporation or in the case of zinc enolates or aza-enolates [98,99]. By contrast, the Ni-mediated carbozincation of di-substituted alkynes such as 91 is more general, but salt-free diorganozincs are necessary and the regioselectivity of the carbozincation reaction is excellent only for arylacetylenes and TMS-substituted acetylenes (Scheme 4.22) [100].…”

The enantioselective construction of tetracyclic diterpene skeletons with Friedel–Crafts alkylation and palladium-catalyzed cycloalkenylation reactions

“…In the process, the strategy would create ring D and the bicyclo[3.2.1]octane at a later stage, after rings A-C have been generated. To the best of our knowledge, this approach has not previously been used with the palladium-catalyzed cycloalkenylation 35–38 . The Friedel-Crafts alkylation would rely on precedent 39–43 and would be the second example of an intramolecular carbon nucleophile conjugate addition to the enone system of the Birch-Cope sequence product; along with the Rauhut-Currier reaction that we have recently communicated 44, 45 .…”