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