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- Title
Stereodivergent Synthesis and Stereochemical Reassignment of the C79-C104 Fragment of Symbiodinolide.
- Authors
Takamura, Hiroyoshi; Fujiwara, Takayuki; Kawakubo, Yohei; Kadota, Isao; Uemura, Daisuke
- Abstract
We have synthesized eight possible diastereoisomers 3 a- h of the C79-C97 fragment of symbiodinolide ( 1) in a stereodivergent manner by utilizing a dithiane addition to the aldehyde as a key step. Comparison of the 13C NMR chemical shifts of the natural product 1 and the synthetic products 3 a- h indicated that the relative stereostructure of this fragment in symbiodinolide ( 1) is that represented in 3 a or f. We have stereodivergently synthesized eight possible diastereoisomers of the C94-C104 fragment 4 a- h, and we have compared their 13C NMR chemical shifts with those of the natural product, which established the relative stereochemistry of this fragment to be that described in diastereoisomers 4 a or e. By combining the stereostructural outcomes of the C79-C97 and C94-C104 fragments, we have proposed four candidate compounds of the C79-C104 fragment 2 a- d. We also synthesized diastereoisomers 2 a and b ( 2 a in the preceding article; Chem. Eur. J. 2015, DOI: 10.1002/chem.201503880) by a Julia-Kocienski olefination and diastereoisomers 2 c and d by a Wittig reaction. By comparing the 13C NMR chemical shifts of natural symbiodinolide ( 1) with those of the synthetic products 2 a- d, we have reassigned the stereostructure of the C79-C104 fragment of natural product 1 to be that depicted in diastereoisomer 2 b.
- Subjects
DIASTEREOISOMERS synthesis; MACROCYCLIC compound synthesis; POLYOL synthesis; NATURAL products; CHEMICAL shift (Nuclear magnetic resonance); NUCLEAR magnetic resonance spectroscopy; WITTIG reaction
- Publication
Chemistry - A European Journal, 2016, Vol 22, Issue 6, p1984
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201503881