jo5b01626_si_001.pdf (11.37 MB)
Stereoselective Iterative Convergent Synthesis of Z‑Oligodiacetylenes from Propargylic Dithioacetals
journal contribution
posted on 2015-09-04, 00:00 authored by Chih-Wei Chen, Kunzeng Fan, Chih-Hsien Chen, Shou-Ling Huang, Yi-Hung Liu, Tsong-Shin Lim, Guan-Wu Wang, Tien-Yau LuhA series
of tBu-substituted Z-oligodiacetylenes
(Z-ODAs) are synthesized
from the reactions of allenyl/propargylic zinc reagents, obtained
from the corresponding propargylic dithiolanes and BuLi, with dithiolane-substituted
propargylic aldehydes followed by stereospecific elimination of β-thioalkoxy
alcohols under Mitsunobu conditions. The stereochemical assignments
are based on NOE experiments. The X-ray structure of the hexamer further
supports the Z configuration for each of the double
bonds in these ODAs. The photophysical properties of these Z-ODAs have been examined and are compared with known related E- and Z-ODAs with different substituents.