TY - JOUR
T1 - 2価のパラジウム触媒を用いる含窒素ヘテロ環の立体選択的な構築と天然物不斉合成への応用
AU - Hirai, Yoshiro
AU - Yokoyama, Hajime
PY - 1998/1
Y1 - 1998/1
N2 - Stereoselective amino-cycloaddition of alkenylamines is one of the most important approaches for the stereoselective construction of nitrogen hetero-alicycles, which form the skeletons of several biologically active natural products and related compounds. We recently developed the intramolecular substitution of an allylic alcohol by a heteroatom using a palladium (II) catalyst without activation of the allylic alcohol. This review describes the stereoselective cyclization of the optically active urethanes and oxazolidinones containing allyl alcohol moiety using bis(acetonitrile)palladium(II) chloride leading to the 2-functionalized 5-hydroxypiperidine, the trans-2,5-disubstituted pyrrolidine, and the trans -2,6-piperidine, respectively. The stereoselective construction of different stereoisomers from similar precursors by changing transition metals (a palladium(II) catalyst → a silver salt) is also described. The cyclo-adducts obtained were proved to be useful chiral building blocks by their conversion into (+)-coniine, (-)-5-hydroxysedamine, (-)-bulgecinine, (+)-prosopinine, and a prospective synthetic intermediate of (+)-palustrine, respectively.
AB - Stereoselective amino-cycloaddition of alkenylamines is one of the most important approaches for the stereoselective construction of nitrogen hetero-alicycles, which form the skeletons of several biologically active natural products and related compounds. We recently developed the intramolecular substitution of an allylic alcohol by a heteroatom using a palladium (II) catalyst without activation of the allylic alcohol. This review describes the stereoselective cyclization of the optically active urethanes and oxazolidinones containing allyl alcohol moiety using bis(acetonitrile)palladium(II) chloride leading to the 2-functionalized 5-hydroxypiperidine, the trans-2,5-disubstituted pyrrolidine, and the trans -2,6-piperidine, respectively. The stereoselective construction of different stereoisomers from similar precursors by changing transition metals (a palladium(II) catalyst → a silver salt) is also described. The cyclo-adducts obtained were proved to be useful chiral building blocks by their conversion into (+)-coniine, (-)-5-hydroxysedamine, (-)-bulgecinine, (+)-prosopinine, and a prospective synthetic intermediate of (+)-palustrine, respectively.
KW - Nitrogen hetero-alicycles
KW - Palladium(II) catalyst
KW - Stereoselective amino-cycloaddition of alkenylamines
KW - trans-2,5-disubstituted pyrrolidine
KW - trans-2,6-disubstituted piperidine
UR - http://www.scopus.com/inward/record.url?scp=18844455772&partnerID=8YFLogxK
U2 - 10.5059/yukigoseikyokaishi.56.34
DO - 10.5059/yukigoseikyokaishi.56.34
M3 - 総説
AN - SCOPUS:18844455772
SN - 0037-9980
VL - 56
SP - 34
EP - 44
JO - Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
JF - Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
IS - 1
ER -