Hydrozirconation methods for natural isobutylamides (anacyclin, pellitorine and its vinylogue) and synthons.

Low pressure vinylation of aryl and vinyl halides via Heck–Mizoroki reactions using ethylene

“…The palladacycle ( 3 ),13a oxime palladacycles15a ( 4 and 5 ) and vinyl bromides 36b ,23 36c ,24 and 36d 25 were prepared according to literature. N,N -Dimethylacetamide was distilled under reduced pressure from CaH 2 before use and stored under nitrogen.…”

Hydrozirconation

“…This property was used for selective monohydrozirconation of conjugated and non-conjugated polyene derivatives (Scheme 8-8) [84][85][86]. The rate of hydrozirconation decreases with increasing substitution on the alkene.…”

“…Terminal heterosubstituted alkynes X-C≡CH such as RO-C≡CH [16,17,[151][152][153], RSe-C≡CH (R= alkyl, aryl) [154][155][156][157], Me 3 Si-C≡CH [158] and R 2 P-C≡CH [159] were regioselectively converted into the (E)-2-ethenylzirconium complexes via hydrozirconation using 1. Terminal diynes could not be cleanly monohydrozirconated; it was necessary to protect one of the two acetylenic forms with EtMgBr/TMSCl to get single addition [85]. Terminal diynes could not be cleanly monohydrozirconated; it was necessary to protect one of the two acetylenic forms with EtMgBr/TMSCl to get single addition [85].…”

“…An unsymmetrical diyne reacts with 1 preferentially at the less-substituted triple bond [85]. An unsymmetrical diyne reacts with 1 preferentially at the less-substituted triple bond [85].…”

“…Dienols with 2 equiv. Alkyl, aryl, silyl [85,112,183,210] and THP [17,153,211,219] ethers are stable under hydrozirconation conditions; side products were observed only with the trimethylsilyl group [220,221]. Alcohols can also be easily converted to ethers.…”