start-ver=1.4
cd-journal=joma
no-vol=22
cd-vols=
no-issue=6
article-no=
start-page=1984
end-page=1996
dt-received=
dt-revised=
dt-accepted=
dt-pub-year=2016
dt-pub=201602
dt-online=
en-article=
kn-article=
en-subject=
kn-subject=
en-title=
kn-title=Stereodivergent Synthesis and Stereochemical Reassignment of the C79-C104 Fragment of Symbiodinolide
en-subtitle=
kn-subtitle=
en-abstract=
kn-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 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.
en-copyright=
kn-copyright=

en-aut-name=TakamuraHiroyoshi
en-aut-sei=Takamura
en-aut-mei=Hiroyoshi
kn-aut-name=
kn-aut-sei=
kn-aut-mei=
aut-affil-num=1
ORCID=

en-aut-name=FujiwaraTakayuki
en-aut-sei=Fujiwara
en-aut-mei=Takayuki
kn-aut-name=
kn-aut-sei=
kn-aut-mei=
aut-affil-num=2
ORCID=

en-aut-name=KawakuboYohei
en-aut-sei=Kawakubo
en-aut-mei=Yohei
kn-aut-name=
kn-aut-sei=
kn-aut-mei=
aut-affil-num=3
ORCID=

en-aut-name=KadotaIsao
en-aut-sei=Kadota
en-aut-mei=Isao
kn-aut-name=
kn-aut-sei=
kn-aut-mei=
aut-affil-num=4
ORCID=

en-aut-name=UemuraDaisuke
en-aut-sei=Uemura
en-aut-mei=Daisuke
kn-aut-name=
kn-aut-sei=
kn-aut-mei=
aut-affil-num=5
ORCID=

affil-num=1
en-affil= Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University
kn-affil=

affil-num=2
en-affil= Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University
kn-affil=

affil-num=3
en-affil= Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University
kn-affil=

affil-num=4
en-affil= Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University
kn-affil=

affil-num=5
en-affil=Department of Chemistry, Faculty of Science, Kanagawa University
kn-affil=
en-keyword=macrocycles
kn-keyword=macrocycles
en-keyword=natural products
kn-keyword=natural products
en-keyword=polyols
kn-keyword=polyols
en-keyword=stereodivergent synthesis
kn-keyword=stereodivergent synthesis
en-keyword=structure elucidation
kn-keyword=structure elucidation
END