Synthesis of tetrasubstituted alkenes by stereo- and regioselective stannyllithiation of diarylacetylenes.
Addition of trimethylstannyllithium to a diarylacetylene takes place exclusively in an anti-fashion to produce a lithio vinylstannane intermediate. The regioselectivity of the addition is controlled by the steric and electronic property of the acetylene and reaches up to >99:1. The two newly formed C-metal bonds can be sequentially and stereospecifically transformed into two new C-C bonds as illustrated by stereoselective synthesis of 4-hydroxytamoxifen and its regioisomer. A tetraarylethene bearing different aryl groups can be synthesized similarly and cyclized to a substituted dibenzo[g,p]chrysene derivative via a palladium-catalyzed arylation reaction.
Tsuji
Hayato
H
Department of Chemistry, School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan. tsuji@chem.s.u-tokyo.ac.jp
Ueda
Yasuyuki
Y
Ilies
Laurean
L
Nakamura
Eiichi
E
D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism; D014001:Tin / Q000737:chemistry*
D000475:Alkenes; D000480:Alkynes; D009942:Organometallic Compounds; D014001:Tin; D008094:Lithium