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ID 56206
フルテキストURL
著者
Takamura, Hiroyoshi Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University
Fujiwara, Takayuki Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University
Kawakubo, Yohei Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University
Kadota, Isao Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University
Uemura, Daisuke Department of Chemistry, Faculty of Science, Kanagawa University
抄録
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 13 C 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 13 C 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 13 C 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.
キーワード
macrocycles
natural products
polyols
stereodivergent synthesis
structure elucidation
備考
This is an article published by WILEY‐VCH
We acknowledge JGC-S Scholarship Foundation, The Naito Foundation, The Sumitomo Foundation, and The Uehara Memorial Foundation for their financial supports. This research was supported by a Grant-in Aid for Scientific Research (No. 24710250) from the Japan Society for the Promotion of Science (JSPS).
発行日
2016-02
出版物タイトル
Chemistry - A European Journal
22巻
6号
出版者
WILEY‐VCH
開始ページ
1984
終了ページ
1996
ISSN
0947-6539
NCID
AA11076269
資料タイプ
学術雑誌論文
言語
English
OAI-PMH Set
岡山大学
著作権者
https://creativecommons.org/licenses/by-nc-nd/4.0/deed.ja
論文のバージョン
author
PubMed ID
DOI
Web of Sience KeyUT
関連URL
isVersionOf https://doi.org/10.1002/chem.201503881