Stereodivergent Synthesis and Stereochemical Reassignment of the C79-C104 Fragment of Symbiodinolide

Hiroyoshi Takamura, Takayuki Fujiwara, Yohei Kawakubo, Isao Kadota, Daisuke Uemura

Research output: Contribution to journalArticle

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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.

Original languageEnglish
Pages (from-to)1984-1996
Number of pages13
JournalChemistry - A European Journal
Volume22
Issue number6
DOIs
Publication statusPublished - Feb 5 2016

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Chemical shift
Biological Products
Nuclear magnetic resonance
Stereochemistry
Aldehydes
symbiodinolide

Keywords

  • macrocycles
  • natural products
  • polyols
  • stereodivergent synthesis
  • structure elucidation

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Stereodivergent Synthesis and Stereochemical Reassignment of the C79-C104 Fragment of Symbiodinolide. / Takamura, Hiroyoshi; Fujiwara, Takayuki; Kawakubo, Yohei; Kadota, Isao; Uemura, Daisuke.

In: Chemistry - A European Journal, Vol. 22, No. 6, 05.02.2016, p. 1984-1996.

Research output: Contribution to journalArticle

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