Synthesis and activity of plant growth-promoting steroids, (22R,23R,24S)-28-homobrassinosteroids, with modifications in rings A and B
Abstract
In order to investigate the structure-activity relationships of brassinosteroids, fourteen (22R,23R,24S)-28-homobrassinosteroids with modifications in rings A and B were synthesized from (22E,24S)-3β-hydroxy-5α-stigmast-22-en-6-one (3a). The (22R,23R)-vicinal diol was introduced by epoxidation of the trans C-22(23) double bond, followed by trans ring-opening of the resulting epoxides by HBr–AcOH, and then an inversion reaction at the carbon bearing bromine by acetoxy anion to give (22R,23R,24S)-3β,22,23-triacetoxy-5α-stigmastan-6-one (8a). Baeyer–Villiger oxidation of (8a) gave the two regioiso-meric 6-oxa- and 7-oxa-lactones (15a) and (16a). Introduction of a 3α-hydroxy group and C-2(3) or C-3(4) double bond was achieved by treatment of the 3β-methanesulphonate (10b), (17b), or (25b) with lithium carbonate in refluxing dimethylformamide. Further elaboration of ring A gave 28-horao-brassinosteroids, 2-deoxybrassinosteroids, 2-deoxy-4α-hydroxybrassinosteroids, and their regioiso-meric 6-oxalactone compounds. Bioassay using the rice-lamina inclination test indicated that the 3α,4α-diol analogue (23) has almost the same activity as the 2α,3α-diol (1b), and the 2-deoxysteroids (13) and (21) were also highly active, showing one-tenth the activity of the 28-homobrassinolide (1b). The following structural features of brassinosteroids are important for the high activity: (i) the (22R,23R)-vicinal diol moiety; (ii) the (24S)-methyl or -ethyl group; (iii) the 7-oxalactone or 6-oxo functionality in the B-ring; (iv) a 3α-hydroxy group, 2α,3α-vicinal diol, or 3α,4α-vicinal diol; and (v) an A,B-trans-fused ring junction.
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The (22S,23S)-28-homobrassinolide (HB) is one of the most active brassinosteroids in inducing plant growth in various plant bioassay systems.
“The (22S,23S)-28-homobrassinolide (HB, Figure 1) is one of the most active brassinosteroids in inducing plant growth in various plant bioassay systems 7.”
From Akt-dependent anabolic activity of natural and synthetic brassinosteroids in rat skeletal muscle cells (2011) · cites this paper as [7]
In plants, moving from the lactone to the 6-ketone decreases brassinolide activity by 50% between brassinolide and castasterone.
“To the contrary, moving from the lactone to the 6-ketone in plants, it was observed that the brassinolide activity decreases by 50% between brassinolide and castasterone 7.”
From Akt-dependent anabolic activity of natural and synthetic brassinosteroids in rat skeletal muscle cells (2011) · cites this paper as [7]
28-Homobrassinolide is almost as active as 24-epibrassinolide in inducing plant growth in various bioassay systems.
“28-Homobrassinolide (HB; Fig. 1A) is almost as active as 24-epibrassinolide in inducing plant growth in various bioassay systems (24).”
From Anabolic effect of plant brassinosteroid (2011) · cites this paper as [24]
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“1A) is almost as active as 24-epibrassinolide in inducing plant growth in various bioassay systems (24).”
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“In this study, we synthesized a set of brassinosteroid analogues of a natural brassinosteroid (22S,23S)homobrassinolide (HB, 1) including (22S,23S)-homocastasterone (2), (22S,23S)-3α-fluorohomobrasinolide (3), (22S,23S)-3α-fluoro-homocastasterone (4), (22S,23S)-7v-azahomobrassinolide (5), (22S,23S)-6-aza-homobrassinol…”
BackgroundMethodYamamoto, S., Watanabe, B., Otsuki, J., et al. (2005) · Bioorganic & Medicinal Chemistry · doi:10.1016/j.bmc.2005.10.024 · Cited by 22 · see citing works
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MethodNew advances in the field of synthesis of natural polyhydroxysteroids
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Self-citationBuckingham, J. (1995) · Springer eBooks · doi:10.1007/978-1-4899-3316-4_20
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- Authors
- Takatsuto, S., & Ikekawa, N.
- Venue
- Journal of the Chemical Society, Perkin Transactions 1
- Publisher
- Royal Society of Chemistry (RSC)
- Published
- 1984
- Pages
- 439
- ISSN
- 1364-5463 (ISSN-L)
- 0300-922X
- OpenAlex
- W2006943457
- Cited by
- 27
- References
- 0
- Citations by year
- 2019: 1 · 2017: 1
- FWCI
- 0.74
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of the Chemical Society Perkin Transactions 1 (publishedVersion)
- Topics
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › Steroid Chemistry and Biochemistry
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › Phytochemical Studies and Bioactivities
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › Plant biochemistry and biosynthesis
- Keywords
- brassinosteroids, structure-activity relationship, 1,2-diols, 28-homobrassinolide, stigmasterol
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