Carotenoid Science Vol 24 2020

11-17Structures of Carotenoids Determined by Our Research Group
During 2009 to 2019
Takashi Maoka*
Research Institute for Production Development, 15 Shimogamo, Morimoto Cho, Sakyoku, Kyoto
606-0805, Japan*Correspondence should be addressed. Tel:+81-75-481-1107, FAX: +81-75-791-7659
E-mail: maoka@mbox.kyoto-inet.or.jp
Abstract： Our research group determined 123 structures of carotenoids during 1978 to 2008. Since
then, structures of 78 carotenoids were newly determined. They were 43 natural products ofcarotenoids, 22 reaction products of carotenoids with reactive oxygen species, and 13 carotenoids
produced by pathway engineering. In this review, structures of 78 carotenoids determined by ourresearch group during this decade were described.
Key Words: structure, new carotenoids
Since 1978, I have contributed structural
studies of various carotenoids. In 2009, I
described the list of 123 carotenoids determinedby our research group during 1978 to 2008 [1].
The next decade, our research group
determined structure of 78 carotenoids,
including 43 naturally occurring compounds,
22 reaction products of carotenoids withreactive oxygen species, and 13 carotenoidsproduced by pathway engineering. In thepresent review, structures of these 78
carotenoids were described. The compounds
numbers are described continuously previousreview [1] according to publishing order.

leaves of rice [3].
OH
H3CO

OCH3O

O

CH3OH
HO

(3R,2'S)-Myxol 2'-fucoside (127)

OH
H3CO

OCH3O

O

CH3HO
OH
HO

(2R,3R,2'S)-2-hydroxymyxol 2'-fucoside (128 )Carotenoids (127) and (128) are isolatedfromcyanobacterium

Nostoccommune

NIES-24 [4].
OHHO

(3'Z,5'Z)-Cellaxanthin (124)

HOON

Lutein-6H-1,2-oxzazine (129)

HONO2
HO

(3'Z,5'Z)-Torulene (125)

Carotenoids (124) and (125) were isolated
from the seeds of oriental bitter sweet Celastrus
orbiculatus [2].

NO2OHHOOH

O
314-s-cis-15-nitro-lutein (130)O

14'-s-cis-15'-nitro-lutein (131)

Carotenoids (129) ~ (131) was obtained asreaction products of lutein with peroxynitrite[5].

Lutein 3-acetate (126)

Carotenoid (126) was found in senescent11

Carotenoid Science Vol 24 2020

11-17OHHOO

HOH 3COHO

82"

CH37"

71"

OHO5"

Deoxyoscillol 2-rhamnoside (132)

OH8" 9" 10"11"

12"
13"

HN

14"

N6"

OH

O

13 "

4"

3"

1" 19"

Carotenoid (132) was isolated
Gemmatimonas aurantiaca [6].

32"

from

21"

19O

O

16" 171"

N

17 16

131"
132"

15"

NH
2"

OHOH

121"

81"

173"

17" 17 "

20'18

O

181"

O

pyropheophorbide A ester (143)

OOH
N

HN

NH

N

O
O

HOLutein 3-pyropheophorbide A ester (144)

ROHOH

4-Ketodeepoxyneoxanthin (133)OH

2: R=a3: R=b4: R=c5: R=dO

Lutein 3'-pyropheophorbide A ester (145)4-Keto-4'-hydroxydiatoxanthin (134)

OOHMutatoxanthin pyropheophorbide A ester (146)Novel carotenoids and pyropheophorbide Aesters (142) ~ (146) were isolated from visceraof abalone [11].

3'HO

Epigobiusxanthin (135)
Stereostructure was revised by Yamano et al. (2015)15NO215'OH

14'HOO

712O 8NO2HOO

7,8-Dihydrodiadinoxanthin (136)12-Nitrocapsanthin (148)(14'Z)-15'-Nitrocapsanthin (147).

OHO

9'OOO

HO

(14Z,9'Z)-15-Nitrofucoxanthin(151)

Carotenoids (147) ~ (151) were obtained as
products of fucoxanthin with peroxynitrite [12].

8'7'OH

8'7'HOOOO

HO

Carotenoids (137) and (138) were isolated
from clams, Ruditapes philippinarum andMeretrix petechialis [9].

HO.

(14Z)-15-Nitrofucoxanthin (149)

Crassostreaxanthin B 3-acetate (138)

7',8',9',10'-Tetrahydro--cryptoxanthin (139)

HOOH

OO

O

HO

15
14O

15NO2.

O

Crassostreaxanthin A 3-acetate (137)

10'NO2(11Z)-11-Nitrofucoxanthin (150)

OO

O

HOO

OH

O

NO2

11O

OOOH

HO

Carotenoids (133) ~ (136) were isolated fromthe crown-of-thorns starfish Acanthaster planci[7]. Stereostructure of epigobiusxanthin (135)
was revised by Y. Yamano, et al [8].

OOHOOHOOHOO

HO19'Fucoxanthin pyropheophorbide A ester (142)

O.

HOO

18"20"

O

16' 17'

15'

107O
53'1'O Halocynthiaxanthin 3'-acetateOHOO

.

5'7'

10'

151O 3220

7',8'-Dihydrodiatoxanthin (140)(3S,6S,6'S)--Cryptoxanthin (141)

Catotenoids (139) ~ (141) were isolated fromthe Japanese common catfish Silurus asotus[10].

12Carotenoid Science Vol 24 2020

11-17OHOO19'OOOH19'-Hexanoyloxyhalocynthiaxanthin
(152)
17'HO

HO

(3R,2'S)-2-Isopentenylsaproxanthin (161)

OO 19OO

Carotenoid (161) was isolated fromyellow-orange bacterium Jejuia pallidilutea
strain 11shimoA1 [18].

O

19-Hexanoyloxycrassostreaxanthin A (153)

HOO 19

O

HOH
3'OO.

HOOH

OH

Carotenoids (152) ~ (154) were from the sea
mussel Mytilus galloprovincialis, grown in theBlack Sea [13].

HO 3

OH
3'(meso)-Alloxanthin (163)

Alloxanthin optical isomers (162) and (163)were found in aquatic animals [19].

OHOO(3S,3'S)-Alloxanthin (162)HO 3

19-Hexanoyloxyallenicmytiloxanthin (154)11-Apoastaxanthinal (155)OHOHOO

Carotenoid (164) was produced in
Escherichia coli through metabolic engineering
using carotenogenic genes of bacterium andliverwort [20].

Carotenoids (155) and (156) were obtained
as auto-oxidation products of astaxanthin [14].
HOO

4-Ketozeinoxanthin (164)O

14'-Apoastaxanthinal (156)(3R)-3-Hydroxy-4-ketotorulene (157)
relative stereostructure was dterminedOH5HOO

6OH(3R)-3-Hydroxy-4-keto--carotene (158)(threo)-Lycopene-5,6-diol (165)

Carotenoids (157) and (158) were isolated
fromtheyeast
Xanthophyllomyces
dendrorhrous [15].

relative stereostructure was dterminedOH
56OH(erythro)-Lycopene-5,6-diol (166)6'

relative stereostructure was dtermined
HO(6'S)--Carotene (159)

1,6-Didehydro-2,6-cyclolycopene-5-ol B (167)

Carotenoid (159) was isolated from unusual
Cyanobacteria with unique chlorophylla [16].
OHOOOHOH

HOOO
OH
OH

3--Glucosyl-3'-quinovosyl zeaxanthin (160)OH

Carotenoid (169) was obtained byEscherichia coli cells expressing thePantoea ananatis carotenoid biosynthesis
gene cluster [17].

13Carotenoid Science Vol 24 202011-17

relative stereostructure was dtermined HO9OH

HO

2',6'-Cyclo--carotene-1',5'-diol A (168)O

relative stereostructure was dtermined HOOH

2',6'-Cyclo--carotene-1',5'-diol B (169)

OOH

relative stereostructure was dterminedOH

9'

HO(threo)--Carotene-5',6'-diol (170)
relative stereostructure was dtermined(9Z,9'Z)-Tetrahydroastaxanthin (178)

OH

Carotenoid (178) from the sea cucumber
Plesiocolochirus minutus [24].

HO(erythro)--Carotene-5',6'-diol (171)O

Carotenoids (165) to (171) were isolated
from
thefritsofgac
Momordicacochinchinensis [21].
21

23

20

96

1

24

17

21

13'

9'

25'

24'

23'

1C50--Carotene (172)
23

20

96

13

17

19

3

13'

9'

20'

25'

22

24'

23'

23

20
1

9

6

20'

13

17

21

13'

9'

9

6

24

24'

23'

13HO
O

22

19

25'

13'

9'

24'

23'

OH

HOOHOO

Astaxanthin 5,8-endperoxide (182)

OO

1'
20'

21'

OO

HO

Carotenoids (172) ~ (175) produced bypathway engineering in Escherichia coli [22].

O9'OHOOOOHCapsanthin 5,8-endperoxide (184)OO

O(6E)-9'-Aporhodoxanthinone (176)6OH

Capsanthin 5,6-endperoxide (183)

HO

O

O

21'

O

C50-Astaxanthin (175)6O
O Astaxanthin 5,6-endperoxide (181)

HO

3'

19'

3

OH

21'

20'

22'

25
17

O

1'C50-Canthaxanthin (174)
23

20
125'

22

Astaxanthin 5,8-epoxide (180)

O

O
1919'

O

O

HOOH

O

22'

25

24

21'

3'

C50-Zeaxanthin (173)
21

OH

1'

19'

HO

O

1'

22'

25

24

Astaxanthin 5,6-epoxide (179)

O

1919'

22O
HO

22'

25

13OH

O
OOO

(6Z)-9'-Aporhodoxanthinone (177)OH

Capsorubin 7,8-epoxide (185)

HO9'OO

Capsorubin 7,8-endperoxide (186)OH

Carotenoids (179) ~ (184) was obtained asreaction products of astaxanthin with reactive
oxygen species [25]. Carotenoids (185) and(186) were obtained as capsanthin andcapsorubin with reactive oxygen species [26] .

Carotenoids (176) and (177) were obtainedin zeaxanthin-synthesizing Escherichia coli byredox stress [23].

14Carotenoid Science Vol 24 2020

11-17OHO

O

Echinenone 5',8'-epoxide (187)

OOH

Isoastaxanthin (195)

OHOOHO

Echinenone 5',6'-epoxide (188)OH

Penaeusxanthin (196)

OHOH

OOO
HOO

3'-Hydroxtechinenone 5',6'-epoxide (189)5,6-Dihydropenaeusxanthin (197)OH

Carotenoids (187) ~ (189) were obtained by
the interaction of the foreign carotenoid
ketolase CrtW and endogenous epoxy
carotenoids unique to sweet potato tubers [27].

OH
OH

HO
OH

(3R,4S,5R,6R,3'R,4'S,5'R,6'R)-Tetrahydroxypirardixanthin (198)
OHOH

OO

-Carotene 5,6-endperoxide (190)

HOOH

O

HOO

OH

O
O

5,6-Dihydrocrustaxanthin (199)

Carotenoids (195) ~ (199) were isolated fromthe prawn Penaeus japonicus and Penaeus
vanamei [30].

-Carotene 5,6-endperoxide (191)

28'
21OH

22

123

52

24

925
13'

9'

27

HOH2C 28O30

Zeaxanthin 5,8-endperoxide (193)

2130

22'

23'

24
13

21'

22'

25
17

19

13'

9'

19'

5
22

25'

24'

23'

5'
1'
20'

21'

2'

27'

30'

CH2OH
26' 28'29'

C60-Sarciniaxanthin (201)

Carotenoids (200) and (201) were obtained
genetically engineering biosynthetic product inEscherichia coli [31].

OHHO

962 12723

2028 26

HOH2C24'

C60-Flavuaxanthin (200)2929

Carotenoids (190) ~ (193) were obtained asreaction products of -Carotene and zeaxanthinwith reactive oxygen species [28].

1'

19'
25'

O

20'

5'
2'

26

CH2OH

27'

26'

19

1320

HO

30'

29'

Zeaxanthin 5,6-endperoxide (192)6'-Epimonadoxanthin (194)

Improvements of analytical instruments suchas NMR, MS, and HPLC have made it possible
to perform the structural elucidation of very
minor (141, 199) or complex structures ofcarotenoids (142~146) in nature. Determinationof complex stereo-structure of carotenoids(165~171) is needed chemical synthetic
approach. Progress of LC/MS, LC/MS/MS
methods can be determined unstablecompounds such as reaction products ofcarotenoids with reactive oxygen species(179~184 and 190~193). These results
indicated that carotenoids scavenged not only
singlet oxygen but also hydroxyradical andsuperoxiide anion radical through chemical
reactions. Furthermore, carotenoids are able tocapture peroxynitrite and nitrogen dioxide
radicals from their molecules to form

Carotenoid (194) was isolated from therosary goby Gymnogobius castaneus [29].

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Carotenoid Science Vol 24 2020

11-17

nitro-carotenoids (129~131 and 147~151).
Pathway
engineering
producedseveralinteresting structural carotenoids, which are notfound in nature.
In conclusion, I determined total 201
carotenoids during for decade as describedabove. I acknowledged all of co-authors of
my publications.

Terada, T. Maoka, J. Oleo Sci. 61, 17-21(2012).
15. T. Maoka, T. Etoh, A. Osawa, K. Shindo, J.
Oleo Sci. 61, 401-406 (2012).
16. S. Takaichi, M. Mochimaru, H. Uchida, A.
Murakami, E. Hirose, T. Maoka, T.
Tsuchiya, M. Mimuro, Plant Cell Physiol.
53, 1881-1888 (2012).
17. S.-K. Choi, A. Osawa, T. Maoka, J. Hattan,
K. Ito, A. Uchiyama, M. Suzuki, K. Shindo,
N. Misawa, Appl Microbiol Biotechnol. 97,8479-8486 (2013).
18. T. Takahashi, K. Nishida, T. Sawabe, T.
Maoka, K. Miyashita, H. Hosokawa, Appl.
Microbiol Biotechnol. 98, 6633-6640(2014).
19. Y. Yamano, T. Maoka, A. Wada, MarineDrugs, 12, 2623-2632 (2014).
20. T. Maoka, M. Takemura, H. Tokuda, N.
Suzuki, N. Misawa, Tetrahedron Lett, 55,6708-6710 (2014).
21. T. Maoka, Y. Yamano, Wada, T. Etho, Y.
Terada, H. Tokuda, H. Nishino, J. Agric.
Food Chem. 63, 1622-1630 (2015).
22. M. Furubayashi, M. Ikezumi, S. Takaichi, T.
Maoka, H. Hemmi, T. Ogawa, K. Saito, A.
V.
Tobias,D.
Umeno,NatureCommunications 6:7534 DOI:10.1038(2015).
23. M. Takemura, T. Moaka, A. Osawa, H.
Higashinaka, H. Shimada, K. Shindo, N.
Misawa, Tetrahedron Lett. 56, 6063-6055(2015).
24. T. Maoka, S. Nakachi, R. Kobayashi, M.
Mori, Y. Sakagami, Tetrahedron Lett. 56,5954-5955 (2015).
25. A. Nishino, T. Maoka, H. Yasui,Tetrahedron Lett. 57, 1967-1970 (2016).
26. A. Nishino, H. Yasui, T. Maoka, J. Agric
Food Chem. 64, 4786-4792 (2016).
27. T. Maoka, M. Otani, M. Z. Khan, M.
Takemura, J. Hattan, No. Misawa,Tetrahedron Lett. 57, 4746-4748 (2016).
28. A. Nishino, H. Yasui, T. Maoka, J. Oleo.
Sci. 66, 77-84 (2017).
29. T. Maoka, J. Oleo Sci. 97, 1259-1263(2018).
30. T. Maoka, Y. Kawashima, M. Takaki. J.
Oleo Sci. 97,1452-1433 (2018).
31. T. Maoka, F. Sunada, I. Kuroda, Y. Oda.
Presented at 33 th Carotenoid Symposium
Japan, Chiba 2019.

References
1. T. Maoka, Carotenoid Science 14, 25-36(2009).
2. T. Maoka, Phytochemistry 70, 920-923(2009).
3. M. Kusaba, T. Maoka, R. Morita, S.
Takaichi, Plant Cell Physiol.50, 1573-1577(2009).
4. S. Takaichi, T. Maoka, M. Mochimaru,Curr Microbiol. 59, 413-419 (2009).
5. M. Tsuboi, H. Etoh, Y. Yomoda, K. Kato, H.
Kato, A. Kulkarni, Y. Terada, T. Maoka , H.
Mori, T. Inakuma, Tetrahedron Lett. 51,676-678 (2010).
6. S. Takaichi, T. Maoka, K. Takasaki, S.
Hanada, Microbiology 156, 757-763(2010).
7. T. Maoka, N. Akimoto,Y. Terada, S.
Komemushi, R. Harada, N. Sameshima, Y.
Sakagami, J. Nat. Prod. 73, 675-678(2010).
8. Y. Yamano, K. Ematsu, H. Kurimoto, T.
Maoka, A. Wada, Mar. Drugs 13, 159-172(2015).
9. T. Maoka, N. Akimoto, M. Murakoshi, K.
Sugiyama, H. Nishino, J. Agric Food Chem.
58, 5784-5788 (2010).
10. T. Maoka N. Akiomoto, Chem. Phram. Bull.
59, 140-145 (2011),
11. T. Maoka, T. Etoh, N. Akimoto, H. Yasui,
Tetrahedron Lett. 52, 3012-3015 (2011).
12. M. Tsuboi, H. Etoh, K. Kato, H.
Nakatugawa, H. Kato, Y. Maejima, G.
Matumoto, H. Mori, M. Hosokawa, K.
Miyashita, H. Tokuda, N. Suzuki, T. Maoka,
J. Agric. Food. Chem. 59, 10872-10578(2011).
13. T. Maoka, T. Etoh, A. V. Borodina, A. A.
Soldatov, J. Agric. Food Chem. 59,13059–13064 (2011).
14. H. Etoh, M. Suhara, S. Tokuyama, H. Kato,
R. Nakahigashi, Y. Maejima, M. Ishikura, Y.

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32. L. Li, M. Furubayashi, S. Wang, T. Maoka,
S. Kawai-Noma, K. Saito, D. Umeno,
ScientificReports,(2019)
9:2982https://doi.org/10.1038/s41598-019-3928w

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