1. Methyl jasmonate analogs 1
Methyl jasmonate (MJA), at first isolated as an important constituents of jasmine absolute, is recently recognized as one of the plant hormones.
MJA and jasmonic acid (JA) sustain many plant actions such as plant growth inhibition, senescence promotion, abscission, tuber formation, stress response etc. Recent studies suggested taht really active compound is its 7-epimer, epijasmonic acid (epiJA). Actually, methyl epijasmonate is epimerized to MJA as 20:1 mixtyure at equilibrium.
We have prepared some MJA analogs with 7-substituents to fix the epimerizaion.
70. Synthesis and Biological Evaluation of Abscisic Acid, Jasmonic Acid and their Analogs"[REVIEW]
　　H. Kiyota, T.i Oritani, S. Kuwahara, "New Discoveries in Agrochemiscals" ACS symposium series No. 892; J. M. Clark, H. Ohkawa eds., pp 246-254 (2005).

15. "Synthesis and Biological Activities of 3,7-and 4,5-Didehydrojasmonates"
　　H. Kiyota, Y. Yoneta and T. Oritani, Phytochemistry, 46, 983-986 (1997).

2. Methyl jasmonate analogs 2
12-Hydroxyepijasmonic acid (tuberonic acid, TA, 4) was isolated as potato tuber-forming substance. On the other hand, its biosynthetic precursor epiJA, and MJA also showed this activity. We prepared 12,12,12-trifluoro-MJA 5 to know the necessity of the OH group of TA, and found that this OH group is not essential for the activity.

10. "Synthesis and Potato Tuber-Inducing Activity of Methyl 5',5',5'-Trifluorojasmonate"
　　H. Kiyota, M. Saitoh, T. Oritani and T. Yoshihara, Phytochemistry, 42, 1259-1262 (1996).

39. "(±)-Methyl 11-Fluorojasmonate as a Designed Antimetabolite of Methyl Jasmonate: Synthesis and Plant Growth Regulatory Activity"
　　H. Kiyota, T. Koike, E. Higashi, Y. Satoh and T. Oritani, J. Pesticide Sci., 26, 96-99.

3. Synthesis of methyl tuberonate (4) Scheme
23. "Synthesis of Methyl Tuberonate, a Potato Tuber-forming Substance"
　　H. Kiyota, D. Nakashima, T. Oritani, Biosci. Biotech. Biochem., 63 (12), 2110-2117 (1999).

4. Preparation of enantiopure methyl jasmonates
A facile method to supply natural and unnnatural enantiomers of methyl jasmonate and its 4,5-didehydro derivative by lipase-catalyzed resolution of racemic methyl 7-epi-cucurbate was developed.
　　

41. "Lipase-catalyzed preparation of both enantiomers of methyl jasmonate"
　　H. Kiyota, E. Higashi, T. Koike, T. Oritani, Tetrahedron: Asymmetry, 12, 1035-1038 (2001).

129. "Enzymatic Resolution of (±)-2-Exo-7-syn-7-(1-propynyl)norbornan-2-ol, a Key Synthetic Intermediate for Jasmonoids"
　　Hiromasa Kiyota, Daisuke Nakashima, Shigefumi Kuwahara, Takayuki Oritani, Zeitschrift fuer Narurforshung, 63b (12), 1441-1442 (2008).

Diastereomeric fluorescent probes for 12-HJA are syntheseized, and the target motor cell protein was detected.
　
(Prof. Minoru Ueda, Dr. Yoko Nakamura, Tetsuya Itabashi (Tohoku Univ.))
95. "Direct Observation of the Target Cell for Jasmonate-type Leaf-closing Factor:Genus-specific Binding of Leaf-movement Factors to the Plant Motor Cell"
　　Y. Nakamura, H. Kiyota, T. Kumagai, M. Ueda, Tetrahedron Lett., 47, 2893-2897 (2006).

67. "Enantio-differential Approach to Identify the Target Cell for Glucosyl Jasmonate-type Leaf-closing Factor, by Using Fluorescence-labeled Probe Compounds"
　　Y. Nakamura, R. Miyatake, A. Matsubara, H. Kiyota, M. Ueda, Tetrahedron, 62, 8805-8813 (2006).

Induction of Differentiation of Human Myeloid Leukemia Cells by Jasmonates 2009.7

Methyl jasomonate and methyl 4,5-didehydrojasmonate induced the differentiation of human leukemia cell lines.
　
(Prof. Yoshio Homma (Shimane Univ.))
　
137. "Gene Expression Profiles in Differentiating Leukemia Cells Induced by Methyl Jasmonate Are Similar to Those of Cytokinins and Methyl Jasmonate Analogs Induce the Differentiation of Human Leukemia Cells in Primary Culture"
　　H. Tsumura, M. Akimoto, H. Kiyota, Y. Ishii, H. Ishikura, Y. Honma, Leukemia, 23 (4), 753-760 (2009).

137. "Gene Expression Profiles in Differentiating Leukemia Cells Induced by Methyl Jasmonate Are Similar to Those of Cytokinins and Methyl Jasmonate Analogs Induce the Differentiation of Human Leukemia Cells in Primary Culture"
　　H. Tsumura, M. Akimoto, H. Kiyota, Y. Ishii, H. Ishikura, Y. Honma, Leukemia, 23 (4), 753-760 (2009).

1. ABA analogs
Abscisic acid is a plant hormone with roles in environmentl stress response, stomatal control of plant water balance, leaf senescense promotion and growth inhibition. However, ready isomerization of the 2Z-double bond by light into trans-ABA results in a significant loss of activity. We synthesized 2E- and 2Z-fluoro-ABA analogs to suppress this isomerization.

70. "Synthesis and Biological Evaluation of Abscisic Acid, Jasmonic Acid and their Analogs" [REVIEW]
T. Oritani, H. Kiyota, S. Kuwahara"New Discoveries in Agrochmicals", ACS Symposium Series, Vol. 892, pp. 246-254 (2005).

59. "Biosynthesis and Metabolism of Abscisic Acid and Related Compounds" [REVIEW]
T. Oritani, H. Kiyota, Nat. Prod. Rep., 20(4), 414-425 (2003).

11. "2-Fluoro and 2-Methoxycarbonyl Epoxy-β-ionylideneacetic Acids as Abscisic Acid Analogs"
　　H. Kiyota, T. Masuda, J. Chiba and T. Oritani, Biosci. Biotech. Biochem., 60(7), 1076-1080 (1996).


2. Preparation of optically active ABA
Among plant hormones, only ABA is not supplied practically because of its high cost. We have developed a praoctical synthesis of (+)-ABA and (+)-beta-ionylideneacetic acid using enzymatic resolution of (±)-phorenol and (±)-beta-cyclogeraniol, respectively.

22. "Hydrolase-Catalyzed Preparation of (R)- and (S)-4-Hydroxy-2,6,6-trimethyl-2-cyclohexen-1-ones (Phorenols), the Key Synthetic Intermediates for Abscisic Acid"
　　H. Kiyota, M. Nakabayashi and T. Oritani, Tetrahedron: Asymmetry, 10 (19), 3811-3818 (1999).

26. "Enzymatic Resolution of (+-)-Epoxy-beta-cyclogeraniol, a Synthetic Precursor for Abscisic Acid Analogs"
　　R. Okazaki, H. Kiyota and T. Oritani, Biosci. Biotech. Biochem., 64 (7), 1444-1447 (2000).