80736-41-0

Basic information

• Product Name: castasterone
• Synonyms: (22R,23R,24S)-2α,3α,22,23-Tetrahydroxy-24-methyl-5α-cholestan-6-one;(22R,23R,24S)-2α,3α,22,23-Tetrahydroxy-5α-ergostane-6-one;(2α,3α,5α,22R,23R,24S)-2,3,22,23-Tetrahydroxyergostan-6-one;BP 214
• CAS NO: 80736-41-0
• Molecular Formula: C₂₈H₄₈O₅
• Molecular Weight: 464.67772
• Product Categories: Bio-Pesticide;Intermediates & Fine Chemicals;Pharmaceuticals;Steroids
• Mol File: 80736-41-0.mol
• Article Data: 18

Chemical Properties

• Melting Point: 259-260 °C
• Boiling Point: 598.7°C at 760 mmHg
• Flash Point: 329.9°C
• Appearance: /
• Density: 1.127g/cm³
• Vapor Pressure: 7.85E-17mmHg at 25°C
• Refractive Index: 1.541
• PKA: 14.29±0.20(Predicted)
• CAS DataBase Reference: castasterone(CAS DataBase Reference)
• NIST Chemistry Reference: castasterone(80736-41-0)
• EPA Substance Registry System: castasterone(80736-41-0)

Safety Data

• Hazardous Substances Data: 80736-41-0(Hazardous Substances Data)

Usage

Description

Castasterone is a plant hormone that belongs to a new class of plant hormones with plant growth-promoting activity. It is isolated from the mature seeds of smooth loofah (Luffa cylindrica (L.) M.J. Roem), along with brassinolide.

Uses

Used in Agriculture:
Castasterone is used as a plant growth regulator for promoting plant growth and development. It enhances various aspects of plant growth, such as cell elongation, division, and differentiation, leading to improved crop yields and quality.
Used in Plant Biotechnology:
In the field of plant biotechnology, castasterone is used as a tool to study the molecular mechanisms underlying plant growth and development. It helps researchers understand the complex signaling pathways and gene regulation involved in plant growth, which can be utilized to develop improved crop varieties with enhanced growth characteristics.
Used in Plant Hormone Research:
Castasterone is also used in plant hormone research to explore its role in plant growth and development, as well as its interactions with other plant hormones. This research can provide valuable insights into the regulation of plant growth and help develop strategies for optimizing plant growth and productivity.

InChI:InChI=1/C28H48O5/c1-14(2)15(3)25(32)26(33)16(4)18-7-8-19-17-11-22(29)21-12-23(30)24(31)13-28(21,6)20(17)9-10-27(18,19)5/h14-21,23-26,30-33H,7-13H2,1-6H3/t15-,16-,17-,18+,19-,20-,21+,23-,24+,25+,26+,27+,28+/m0/s1

Synthetic route

(1R,3aS,3bS,5aS,6aS,9aR,10aR,10bS,12aS)-1-{(S)-1-[(4R,5R)-5-((S)-1,2-Dimethyl-propyl)-2,2-dimethyl-[1,3]dioxolan-4-yl]-ethyl}-8,8,10a,12a-tetramethyl-hexadecahydro-7,9-dioxa-dicyclopenta[a,h]phenanthren-5-one (111118-49-1) → castasterone (80736-41-0)

Conditions	Yield
With trifluoroacetic acid In methanol for 1h;	98%

(20S,22R,23R,24S)-23-(1-ethoxyethoxy)-6-ethylenedioxy-2α,3α-isopropylidenedioxy-5α-ergostan-22-ol (129824-69-7) → castasterone (80736-41-0)

Conditions	Yield
With hydrogenchloride In tetrahydrofuran for 3h; Heating;	94%
With hydrogenchloride In tetrahydrofuran	93.5%

2,3,22,23-tetra-O-acetylcastasterone (77027-48-6) → castasterone (80736-41-0)

Conditions	Yield
With potassium hydroxide for 1h; Heating;	94%

Δ2-(22R,23R,24S)-22,23-dihydroxy-24-methyl-5α-cholestan-6-one (130549-19-8) → castasterone (80736-41-0)

Conditions	Yield
With osmium(VIII) oxide; 4-methylmorpholine N-oxide In tetrahydrofuran; water; tert-butyl alcohol for 22h; Ambient temperature;	93%
With osmium(VIII) oxide; sulfuric acid; sodium sulfite 1.) pyridine, 15 min, 2.) pyridine, 30 min; Yield given. Multistep reaction;

(2R,3S,5α,22R,23R,24S)-6,6-Ethylenedioxy-2,3-isopropylidenedioxyergostane-22,23-diol (91708-76-8) → castasterone (80736-41-0)

Conditions	Yield
With acetic acid at 50℃; for 0.5h;	82%
With acetic acid In water at 50 - 60℃; for 1h;	7.62 g
With acid Yield given;

(22E,24S)-5α-ergost-2,22-dien-6-one (80779-45-9) → castasterone (80736-41-0)

Conditions	Yield
With (3a,9R,3'''a,4'"b,9'"R)-9,9'-[1,4-phthalazinediylbis(oxy)]bis[6'-(methyloxy)-10,11-dihydrocinchonan]; osmium(VIII) oxide; methanesulfonamide; potassium carbonate; potassium hexacyanoferrate(III) In water; tert-butyl alcohol for 15h; Ambient temperature;	80%

(22E)-24α-methyl-5α-cholesta-2,22-dien-6-one (72050-68-1, 80779-45-9, 95343-48-9, 116405-04-0, 147200-25-7) → C28H48O5 + castasterone (80736-41-0)

Conditions	Yield
With potassium osmate(VI) dihydrate; methanesulfonamide; potassium carbonate; potassium hexacyanoferrate(III); hydroquinidine (anthraquinone-1,4-diyl) diether In water; tert-butyl alcohol at 20℃; for 48h;	A n/a B 63%

trimethylaluminum (75-24-1) + (2R, 3S, 22R, 23S, 24R)-23,24-epoxy-6,6-ethylenedioxy-22-hydroxy-2,3-isopropylidenedioxy-5α-cholestane (86413-56-1) → castasterone (80736-41-0)

Conditions	Yield
With n-butyllithium; acetic acid 1) n-hexane, 69 h, room temperature; 2) 50 deg C, 30 min; Yield given. Multistep reaction;

(2R,3S,5S,8S,9S,10R,13S,14S,17R)-17-{(S)-1-[(4R,5R)-5-((S)-1,2-Dimethyl-propyl)-2,2-dimethyl-[1,3]dioxolan-4-yl]-ethyl}-2,3-dihydroxy-10,13-dimethyl-hexadecahydro-cyclopenta[a]phenanthren-6-one (83066-72-2) → castasterone (80736-41-0)

Conditions	Yield
With acetic acid In water at 65℃; for 4h; Yield given;

(22R,23R,24S)-22,23-diacetoxy-2α,3α-isopropylidenedioxy-5α-ergostan-6-one (106560-75-2) → castasterone (80736-41-0)

Conditions	Yield
With sodium hydroxide In methanol for 3h; Heating;	458 mg

(22E,24S)-3α,5-cyclo-5α-ergost-22-en-6-one (80779-43-7) → castasterone (80736-41-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: 82 percent / pyridinium tolunen-p-sulfonate, LiBr / N,N-dimethyl-acetamide / 5 h / 160 °C 2: 80 percent / OsO4, K3, 1,4-bis(0-O-dihydroquinidinyl)phthalazine, K2CO3, methanesulfonamide / 2-methyl-propan-2-ol; H2O / 15 h / Ambient temperature View Scheme

(20S)-6-(1,3-dioxolan-2-yl)-3α,5-cyclo-20-formyl-5α-pregnane → castasterone (80736-41-0)

Conditions

Yield

Multi-step reaction with 8 steps 1: 57 percent / tetrahydrofuran / 1 h / Ambient temperature 2: 98 percent / propionic acid / xylene / 2 h / Heating 3: LiAlH4 / tetrahydrofuran / 2 h / Heating 4: Et3N / toluene / 2 h / 0 °C 5: LiAlH4 / tetrahydrofuran / Ambient temperature 6: 99 percent / 1 M H2SO4 / acetone / 2 h / Ambient temperature 7: 82 percent / pyridinium tolunen-p-sulfonate, LiBr / N,N-dimethyl-acetamide / 5 h / 160 °C 8: 80 percent / OsO4, K3, 1,4-bis(0-O-dihydroquinidinyl)phthalazine, K2CO3, methanesulfonamide / 2-methyl-propan-2-ol; H2O / 15 h / Ambient temperature View Scheme

(22S,23Z)-6-(1,3-dioxolan-2-yl)-3α,5-cyclo-26,27-bisnor-5α-cholest-23-en-22-ol (199169-93-2) → castasterone (80736-41-0)

Conditions

Yield

Multi-step reaction with 7 steps 1: 98 percent / propionic acid / xylene / 2 h / Heating 2: LiAlH4 / tetrahydrofuran / 2 h / Heating 3: Et3N / toluene / 2 h / 0 °C 4: LiAlH4 / tetrahydrofuran / Ambient temperature 5: 99 percent / 1 M H2SO4 / acetone / 2 h / Ambient temperature 6: 82 percent / pyridinium tolunen-p-sulfonate, LiBr / N,N-dimethyl-acetamide / 5 h / 160 °C 7: 80 percent / OsO4, K3, 1,4-bis(0-O-dihydroquinidinyl)phthalazine, K2CO3, methanesulfonamide / 2-methyl-propan-2-ol; H2O / 15 h / Ambient temperature View Scheme

(24S)-6-(1,3-dioxolane-2-yl)-24-methyl-3α,5-cyclo-5α-cholest-22-ene (199169-95-4) → castasterone (80736-41-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: 99 percent / 1 M H2SO4 / acetone / 2 h / Ambient temperature 2: 82 percent / pyridinium tolunen-p-sulfonate, LiBr / N,N-dimethyl-acetamide / 5 h / 160 °C 3: 80 percent / OsO4, K3, 1,4-bis(0-O-dihydroquinidinyl)phthalazine, K2CO3, methanesulfonamide / 2-methyl-propan-2-ol; H2O / 15 h / Ambient temperature View Scheme

C30H48O3 → castasterone (80736-41-0)

Conditions

Yield

Multi-step reaction with 5 steps 1: Et3N / toluene / 2 h / 0 °C 2: LiAlH4 / tetrahydrofuran / Ambient temperature 3: 99 percent / 1 M H2SO4 / acetone / 2 h / Ambient temperature 4: 82 percent / pyridinium tolunen-p-sulfonate, LiBr / N,N-dimethyl-acetamide / 5 h / 160 °C 5: 80 percent / OsO4, K3, 1,4-bis(0-O-dihydroquinidinyl)phthalazine, K2CO3, methanesulfonamide / 2-methyl-propan-2-ol; H2O / 15 h / Ambient temperature View Scheme

(22E,24R)-6-(1,3-dioxolan-2-yl)-24-methyl-3α,5-cyclo-5α-cholest-22-en-26-oic acid ethyl ester (199169-94-3) → castasterone (80736-41-0)

Conditions

Yield

Multi-step reaction with 6 steps 1: LiAlH4 / tetrahydrofuran / 2 h / Heating 2: Et3N / toluene / 2 h / 0 °C 3: LiAlH4 / tetrahydrofuran / Ambient temperature 4: 99 percent / 1 M H2SO4 / acetone / 2 h / Ambient temperature 5: 82 percent / pyridinium tolunen-p-sulfonate, LiBr / N,N-dimethyl-acetamide / 5 h / 160 °C 6: 80 percent / OsO4, K3, 1,4-bis(0-O-dihydroquinidinyl)phthalazine, K2CO3, methanesulfonamide / 2-methyl-propan-2-ol; H2O / 15 h / Ambient temperature View Scheme

(22E,24R)-6-(1,3-dioxolan-2-yl)-26-methanesulfonyloxy-24-methyl-3α,5-cyclo-5α-cholest-22-ene (199169-96-5) → castasterone (80736-41-0)

Conditions

Yield

Multi-step reaction with 4 steps 1: LiAlH4 / tetrahydrofuran / Ambient temperature 2: 99 percent / 1 M H2SO4 / acetone / 2 h / Ambient temperature 3: 82 percent / pyridinium tolunen-p-sulfonate, LiBr / N,N-dimethyl-acetamide / 5 h / 160 °C 4: 80 percent / OsO4, K3, 1,4-bis(0-O-dihydroquinidinyl)phthalazine, K2CO3, methanesulfonamide / 2-methyl-propan-2-ol; H2O / 15 h / Ambient temperature View Scheme

3-methyl-butan-2-one (563-80-4) + ethyl halide → castasterone (80736-41-0)

Conditions	Yield
Multi-step reaction with 10 steps 1: Br2 / methanol 2: acetone / 18 h / Heating 3: NaH / tetrahydrofuran / 0.5 h / 25 °C 4: 80 percent / LDA / tetrahydrofuran / 1.) -40 to -50 deg C, 30 min, 2.) -75 deg C, 14 h 5: 83 percent / H2, pyridine / 10percent Pd/C / ethanol; tetrahydrofuran / 14 h / 2585.7 Torr / Ambient temperature 6: 99 percent / LAH / tetrahydrofuran / 1.) r.t. 2 h, 2.) reflux, overnight 7: 96 percent / CSA / 24 h / Ambient temperature 8: 91 percent / CrO3, pyridine / CH2Cl2 / 48 h / Ambient temperature 9: 72 percent / <(C6H5)3P>3RhCl / benzene / 5 h / Heating 10: 98 percent / aq. TFA / methanol / 1 h View Scheme
Multi-step reaction with 10 steps 1: Br2 / methanol 2: acetone / 18 h / Heating 3: 1.) NaH, triethylphosphonoacetate, 2.) aq. KOH / 1.) THF, 25 deg C, 30 min, 2.) 25 deg C, 24 h 4: 80 percent / LDA / tetrahydrofuran / 1.) -40 to -50 deg C, 30 min, 2.) -75 deg C, 14 h 5: 83 percent / H2, pyridine / 10percent Pd/C / ethanol; tetrahydrofuran / 14 h / 2585.7 Torr / Ambient temperature 6: 99 percent / LAH / tetrahydrofuran / 1.) r.t. 2 h, 2.) reflux, overnight 7: 96 percent / CSA / 24 h / Ambient temperature 8: 91 percent / CrO3, pyridine / CH2Cl2 / 48 h / Ambient temperature 9: 72 percent / <(C6H5)3P>3RhCl / benzene / 5 h / Heating 10: 98 percent / aq. TFA / methanol / 1 h View Scheme

4-(1-methylethyl)furan-2(5H)-one (10547-89-4) → castasterone (80736-41-0)

Conditions

Yield

Multi-step reaction with 7 steps 1: 80 percent / LDA / tetrahydrofuran / 1.) -40 to -50 deg C, 30 min, 2.) -75 deg C, 14 h 2: 83 percent / H2, pyridine / 10percent Pd/C / ethanol; tetrahydrofuran / 14 h / 2585.7 Torr / Ambient temperature 3: 99 percent / LAH / tetrahydrofuran / 1.) r.t. 2 h, 2.) reflux, overnight 4: 96 percent / CSA / 24 h / Ambient temperature 5: 91 percent / CrO3, pyridine / CH2Cl2 / 48 h / Ambient temperature 6: 72 percent / <(C6H5)3P>3RhCl / benzene / 5 h / Heating 7: 98 percent / aq. TFA / methanol / 1 h View Scheme

1-(acetyloxy)-3-methyl-2-butanone (36960-07-3) → castasterone (80736-41-0)

Conditions	Yield
Multi-step reaction with 8 steps 1: NaH / tetrahydrofuran / 0.5 h / 25 °C 2: 80 percent / LDA / tetrahydrofuran / 1.) -40 to -50 deg C, 30 min, 2.) -75 deg C, 14 h 3: 83 percent / H2, pyridine / 10percent Pd/C / ethanol; tetrahydrofuran / 14 h / 2585.7 Torr / Ambient temperature 4: 99 percent / LAH / tetrahydrofuran / 1.) r.t. 2 h, 2.) reflux, overnight 5: 96 percent / CSA / 24 h / Ambient temperature 6: 91 percent / CrO3, pyridine / CH2Cl2 / 48 h / Ambient temperature 7: 72 percent / <(C6H5)3P>3RhCl / benzene / 5 h / Heating 8: 98 percent / aq. TFA / methanol / 1 h View Scheme
Multi-step reaction with 8 steps 1: 1.) NaH, triethylphosphonoacetate, 2.) aq. KOH / 1.) THF, 25 deg C, 30 min, 2.) 25 deg C, 24 h 2: 80 percent / LDA / tetrahydrofuran / 1.) -40 to -50 deg C, 30 min, 2.) -75 deg C, 14 h 3: 83 percent / H2, pyridine / 10percent Pd/C / ethanol; tetrahydrofuran / 14 h / 2585.7 Torr / Ambient temperature 4: 99 percent / LAH / tetrahydrofuran / 1.) r.t. 2 h, 2.) reflux, overnight 5: 96 percent / CSA / 24 h / Ambient temperature 6: 91 percent / CrO3, pyridine / CH2Cl2 / 48 h / Ambient temperature 7: 72 percent / <(C6H5)3P>3RhCl / benzene / 5 h / Heating 8: 98 percent / aq. TFA / methanol / 1 h View Scheme

(22E)-stigmasta-2,22-dien-6-one (74174-45-1) → castasterone (80736-41-0)

Conditions

Yield

Multi-step reaction with 11 steps 1: 72 percent / OsO4, NMO, H2O / acetone; 2-methyl-propan-2-ol / 12 h / Ambient temperature 2: 98 percent / CSA / acetonitrile; CH2Cl2 / 1 h / Ambient temperature 3: OsO4, NMO, aq. NaHCO3, MeSO2NH2 / tetrahydrofuran; 2-methyl-propan-2-ol / 144 h / 40 °C 4: 82 percent / pyridine, NaHCO3, H5IO6 / tetrahydrofuran / 24 h / Ambient temperature 5: 80 percent / LDA / tetrahydrofuran / 1.) -40 to -50 deg C, 30 min, 2.) -75 deg C, 14 h 6: 83 percent / H2, pyridine / 10percent Pd/C / ethanol; tetrahydrofuran / 14 h / 2585.7 Torr / Ambient temperature 7: 99 percent / LAH / tetrahydrofuran / 1.) r.t. 2 h, 2.) reflux, overnight 8: 96 percent / CSA / 24 h / Ambient temperature 9: 91 percent / CrO3, pyridine / CH2Cl2 / 48 h / Ambient temperature 10: 72 percent / <(C6H5)3P>3RhCl / benzene / 5 h / Heating 11: 98 percent / aq. TFA / methanol / 1 h View Scheme

(22E,24S)-3β,5-cyclo-24-ethylcholest-22-en-6-one (74174-49-5) → castasterone (80736-41-0)

Conditions

Yield

Multi-step reaction with 12 steps 1: 80 percent / pyridine hydrochloride, LiBr / N,N-dimethyl-acetamide / 4 h / 160 °C 2: 72 percent / OsO4, NMO, H2O / acetone; 2-methyl-propan-2-ol / 12 h / Ambient temperature 3: 98 percent / CSA / acetonitrile; CH2Cl2 / 1 h / Ambient temperature 4: OsO4, NMO, aq. NaHCO3, MeSO2NH2 / tetrahydrofuran; 2-methyl-propan-2-ol / 144 h / 40 °C 5: 82 percent / pyridine, NaHCO3, H5IO6 / tetrahydrofuran / 24 h / Ambient temperature 6: 80 percent / LDA / tetrahydrofuran / 1.) -40 to -50 deg C, 30 min, 2.) -75 deg C, 14 h 7: 83 percent / H2, pyridine / 10percent Pd/C / ethanol; tetrahydrofuran / 14 h / 2585.7 Torr / Ambient temperature 8: 99 percent / LAH / tetrahydrofuran / 1.) r.t. 2 h, 2.) reflux, overnight 9: 96 percent / CSA / 24 h / Ambient temperature 10: 91 percent / CrO3, pyridine / CH2Cl2 / 48 h / Ambient temperature 11: 72 percent / <(C6H5)3P>3RhCl / benzene / 5 h / Heating 12: 98 percent / aq. TFA / methanol / 1 h View Scheme

(22E,24S)-2α,3α-dihydroxy-5α-stigmast-22-en-6-one (81481-12-1) → castasterone (80736-41-0)

Conditions

Yield

Multi-step reaction with 10 steps 1: 98 percent / CSA / acetonitrile; CH2Cl2 / 1 h / Ambient temperature 2: OsO4, NMO, aq. NaHCO3, MeSO2NH2 / tetrahydrofuran; 2-methyl-propan-2-ol / 144 h / 40 °C 3: 82 percent / pyridine, NaHCO3, H5IO6 / tetrahydrofuran / 24 h / Ambient temperature 4: 80 percent / LDA / tetrahydrofuran / 1.) -40 to -50 deg C, 30 min, 2.) -75 deg C, 14 h 5: 83 percent / H2, pyridine / 10percent Pd/C / ethanol; tetrahydrofuran / 14 h / 2585.7 Torr / Ambient temperature 6: 99 percent / LAH / tetrahydrofuran / 1.) r.t. 2 h, 2.) reflux, overnight 7: 96 percent / CSA / 24 h / Ambient temperature 8: 91 percent / CrO3, pyridine / CH2Cl2 / 48 h / Ambient temperature 9: 72 percent / <(C6H5)3P>3RhCl / benzene / 5 h / Heating 10: 98 percent / aq. TFA / methanol / 1 h View Scheme

(22E,24S)-2α,3α-Dihydroxy-5α-stigmast-22-en-6-one 2,3-acetonide (81481-13-2) → castasterone (80736-41-0)

Conditions	Yield
Multi-step reaction with 9 steps 1: OsO4, NMO, aq. NaHCO3, MeSO2NH2 / tetrahydrofuran; 2-methyl-propan-2-ol / 144 h / 40 °C 2: 82 percent / pyridine, NaHCO3, H5IO6 / tetrahydrofuran / 24 h / Ambient temperature 3: 80 percent / LDA / tetrahydrofuran / 1.) -40 to -50 deg C, 30 min, 2.) -75 deg C, 14 h 4: 83 percent / H2, pyridine / 10percent Pd/C / ethanol; tetrahydrofuran / 14 h / 2585.7 Torr / Ambient temperature 5: 99 percent / LAH / tetrahydrofuran / 1.) r.t. 2 h, 2.) reflux, overnight 6: 96 percent / CSA / 24 h / Ambient temperature 7: 91 percent / CrO3, pyridine / CH2Cl2 / 48 h / Ambient temperature 8: 72 percent / <(C6H5)3P>3RhCl / benzene / 5 h / Heating 9: 98 percent / aq. TFA / methanol / 1 h View Scheme
Multi-step reaction with 8 steps 1: 83.0 g / p-TsOH / 3 h / Heating 2: 30 g / ozone, NaHCO3 / methanol; CH2Cl2 / 2 h / -60 - -50 °C 3: n-BuLi / tetrahydrofuran; hexane / -50 to -60 deg C; -40 deg C, 1 h; -68 to - 65 deg C, 1 h; 0 deg C 4: 74.6 percent / 1.) triphenylphosphine, benzoic acid, diethyl azodicarboxylate; 2.) K2CO3 / 1.) THF, 5-10 deg C, 30 min; 2.) THF/methanol, reflux, 3 h 5: 44.3 g / H2, 1M NaBH4, ethylenediamine, nickel acetate / aq. ethanol / 5 h 6: 93 percent / m-chloroperbenzoic acid, Na2HPO4 / CH2Cl2 / 20 h / 5 °C 7: n-BuLi / hexane; cyclohexane / -70 deg C, 1 h; 10 deg C, 4 h 8: 7.62 g / 80percent AcOH / H2O / 1 h / 50 - 60 °C View Scheme
Multi-step reaction with 7 steps 1: 83.0 g / p-TsOH / 3 h / Heating 2: 30 g / ozone, NaHCO3 / methanol; CH2Cl2 / 2 h / -60 - -50 °C 3: 26.93 g / n-BuLi / tetrahydrofuran; hexane / -50 to -60 deg C; -40 deg C, 1 h; -68 to - 65 deg C, 1 h; 0 deg C 4: 44.3 g / H2, 1M NaBH4, ethylenediamine, nickel acetate / aq. ethanol / 5 h 5: 93 percent / m-chloroperbenzoic acid, Na2HPO4 / CH2Cl2 / 20 h / 5 °C 6: n-BuLi / hexane; cyclohexane / -70 deg C, 1 h; 10 deg C, 4 h 7: 7.62 g / 80percent AcOH / H2O / 1 h / 50 - 60 °C View Scheme

(22E,24S)-24-ethyl-3α,5-cyclo-5α-cholest-22-en-6-ol (103881-47-6) → castasterone (80736-41-0)

Conditions

Yield

Multi-step reaction with 13 steps 1: CrO3, H2SO4 / acetone 2: 80 percent / pyridine hydrochloride, LiBr / N,N-dimethyl-acetamide / 4 h / 160 °C 3: 72 percent / OsO4, NMO, H2O / acetone; 2-methyl-propan-2-ol / 12 h / Ambient temperature 4: 98 percent / CSA / acetonitrile; CH2Cl2 / 1 h / Ambient temperature 5: OsO4, NMO, aq. NaHCO3, MeSO2NH2 / tetrahydrofuran; 2-methyl-propan-2-ol / 144 h / 40 °C 6: 82 percent / pyridine, NaHCO3, H5IO6 / tetrahydrofuran / 24 h / Ambient temperature 7: 80 percent / LDA / tetrahydrofuran / 1.) -40 to -50 deg C, 30 min, 2.) -75 deg C, 14 h 8: 83 percent / H2, pyridine / 10percent Pd/C / ethanol; tetrahydrofuran / 14 h / 2585.7 Torr / Ambient temperature 9: 99 percent / LAH / tetrahydrofuran / 1.) r.t. 2 h, 2.) reflux, overnight 10: 96 percent / CSA / 24 h / Ambient temperature 11: 91 percent / CrO3, pyridine / CH2Cl2 / 48 h / Ambient temperature 12: 72 percent / <(C6H5)3P>3RhCl / benzene / 5 h / Heating 13: 98 percent / aq. TFA / methanol / 1 h View Scheme

1-bromo-3-methyl-2-butanone (19967-55-6) → castasterone (80736-41-0)

Conditions	Yield
Multi-step reaction with 9 steps 1: acetone / 18 h / Heating 2: NaH / tetrahydrofuran / 0.5 h / 25 °C 3: 80 percent / LDA / tetrahydrofuran / 1.) -40 to -50 deg C, 30 min, 2.) -75 deg C, 14 h 4: 83 percent / H2, pyridine / 10percent Pd/C / ethanol; tetrahydrofuran / 14 h / 2585.7 Torr / Ambient temperature 5: 99 percent / LAH / tetrahydrofuran / 1.) r.t. 2 h, 2.) reflux, overnight 6: 96 percent / CSA / 24 h / Ambient temperature 7: 91 percent / CrO3, pyridine / CH2Cl2 / 48 h / Ambient temperature 8: 72 percent / <(C6H5)3P>3RhCl / benzene / 5 h / Heating 9: 98 percent / aq. TFA / methanol / 1 h View Scheme
Multi-step reaction with 9 steps 1: acetone / 18 h / Heating 2: 1.) NaH, triethylphosphonoacetate, 2.) aq. KOH / 1.) THF, 25 deg C, 30 min, 2.) 25 deg C, 24 h 3: 80 percent / LDA / tetrahydrofuran / 1.) -40 to -50 deg C, 30 min, 2.) -75 deg C, 14 h 4: 83 percent / H2, pyridine / 10percent Pd/C / ethanol; tetrahydrofuran / 14 h / 2585.7 Torr / Ambient temperature 5: 99 percent / LAH / tetrahydrofuran / 1.) r.t. 2 h, 2.) reflux, overnight 6: 96 percent / CSA / 24 h / Ambient temperature 7: 91 percent / CrO3, pyridine / CH2Cl2 / 48 h / Ambient temperature 8: 72 percent / <(C6H5)3P>3RhCl / benzene / 5 h / Heating 9: 98 percent / aq. TFA / methanol / 1 h View Scheme

(20S)-2α,3α-isopropylidenedioxy-5α-pregnan-6-one-20-carbaldehyde (174656-33-8) → castasterone (80736-41-0)

Conditions

Yield

Multi-step reaction with 7 steps 1: 80 percent / LDA / tetrahydrofuran / 1.) -40 to -50 deg C, 30 min, 2.) -75 deg C, 14 h 2: 83 percent / H2, pyridine / 10percent Pd/C / ethanol; tetrahydrofuran / 14 h / 2585.7 Torr / Ambient temperature 3: 99 percent / LAH / tetrahydrofuran / 1.) r.t. 2 h, 2.) reflux, overnight 4: 96 percent / CSA / 24 h / Ambient temperature 5: 91 percent / CrO3, pyridine / CH2Cl2 / 48 h / Ambient temperature 6: 72 percent / <(C6H5)3P>3RhCl / benzene / 5 h / Heating 7: 98 percent / aq. TFA / methanol / 1 h View Scheme

(3S,4R,5R,6S)-6-((1R,3aS,3bS,5aS,6aS,9aR,10aR,10bS,12aS)-5-Hydroxy-8,8,10a,12a-tetramethyl-hexadecahydro-7,9-dioxa-dicyclopenta[a,h]phenanthren-1-yl)-3-isopropyl-heptane-1,4,5-triol → castasterone (80736-41-0)

Conditions	Yield
Multi-step reaction with 4 steps 1: 96 percent / CSA / 24 h / Ambient temperature 2: 91 percent / CrO3, pyridine / CH2Cl2 / 48 h / Ambient temperature 3: 72 percent / <(C6H5)3P>3RhCl / benzene / 5 h / Heating 4: 98 percent / aq. TFA / methanol / 1 h View Scheme

(1R,3aS,3bS,5aS,6aS,9aR,10aR,10bS,12aS)-1-((S)-1-{(4R,5R)-5-[(S)-1-(2-Hydroxy-ethyl)-2-methyl-propyl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-ethyl)-8,8,10a,12a-tetramethyl-hexadecahydro-7,9-dioxa-dicyclopenta[a,h]phenanthren-5-ol → castasterone (80736-41-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: 91 percent / CrO3, pyridine / CH2Cl2 / 48 h / Ambient temperature 2: 72 percent / <(C6H5)3P>3RhCl / benzene / 5 h / Heating 3: 98 percent / aq. TFA / methanol / 1 h View Scheme

(S)-3-{(4R,5R)-2,2-Dimethyl-5-[(S)-1-((1R,3aS,3bS,5aS,6aS,9aR,10aR,10bS,12aS)-8,8,10a,12a-tetramethyl-5-oxo-hexadecahydro-7,9-dioxa-dicyclopenta[a,h]phenanthren-1-yl)-ethyl]-[1,3]dioxolan-4-yl}-4-methyl-pentanal (174656-38-3) → castasterone (80736-41-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: 72 percent / <(C6H5)3P>3RhCl / benzene / 5 h / Heating 2: 98 percent / aq. TFA / methanol / 1 h View Scheme

castasterone (80736-41-0) + acetic anhydride (108-24-7) → 2,3,22,23-tetra-O-acetylcastasterone (77027-48-6)

Conditions	Yield
With pyridine; dmap	100%
With dmap In pyridine for 15h; Ambient temperature;	98%
With dmap In pyridine at 20℃; for 15h;	98%

castasterone (80736-41-0) → 6α-hydroxycastasterone (220566-70-1) + 6β-hydroxycastasterone

Conditions	Yield
With sodium tetrahydroborate In methanol at 20℃; Reduction;	A 19% B 77%
With ethanol; sodium for 2h; Reduction; Heating;	A 53% B 10%

castasterone (80736-41-0) → (3α,5α,6α,8β,9α,12β,13β,16α,17β)-10-[(2'α,3'β,4'β,5'β)-3,4-dihydroxy-5,6-dimethyl-2-heptanyl]-5,6-dihydroxy-7a,9a-dimethylhexadecahydro-3H-benzo[c]indeno[5,4-e]oxepin-3-one (72962-43-7)

Conditions	Yield
Yield given. Multistep reaction;
Multi-step reaction with 2 steps 1: pyridine, N,N-dimethylaminopyridine View Scheme

castasterone (80736-41-0) → 6-deoxo-castasteron (87833-54-3)

Conditions	Yield
With potassium hydroxide; hydrazine hydrate In diethylene glycol for 2h; Heating;	1.7 mg

castasterone (80736-41-0) → 6α-hydroxycastasterone (220566-70-1)

Conditions	Yield
With ammonia In tetrahydrofuran; methanol at -78℃; for 2h;	39 mg

castasterone (80736-41-0) + 2,2-dimethoxy-propane (77-76-9) → (1R,3aS,3bS,5aS,6aS,9aR,10aR,10bS,12aS)-1-{(S)-1-[(4R,5S)-5-((S)-1,2-Dimethyl-propyl)-2,2-dimethyl-[1,3]dioxolan-4-yl]-ethyl}-8,8,10a,12a-tetramethyl-hexadecahydro-7,9-dioxa-dicyclopenta[a,h]phenanthren-5-one

Conditions	Yield
With toluene-4-sulfonic acid In dichloromethane Ambient temperature;

castasterone (80736-41-0) → Acetic acid (1R,3aS,3bS,6aS,8S,9R,10aR,10bS,12aS)-8-acetoxy-1-((1S,2R,3R,4S)-2,3-diacetoxy-1,4,5-trimethyl-hexyl)-10a,12a-dimethyl-5-oxo-6-trimethylsilanyl-octadecahydro-benzo[3,4]cyclohepta[1,2-e]inden-9-yl ester

Conditions	Yield
Multi-step reaction with 2 steps 1: 98 percent / 4-DMAP / pyridine / 15 h / 20 °C 2: BF3*Et2O / hexane; CH2Cl2 / 2.5 h / -20 - -15 °C View Scheme

castasterone (80736-41-0) → Acetic acid (1R,3aS,3bS,5S,6aS,8S,9R,10aR,10bS,12aS)-8-acetoxy-1-((1S,2R,3R,4S)-2,3-diacetoxy-1,4,5-trimethyl-hexyl)-10a,12a-dimethyl-6-oxo-5-trimethylsilanyl-octadecahydro-benzo[3,4]cyclohepta[1,2-e]inden-9-yl ester

Conditions	Yield
Multi-step reaction with 2 steps 1: 98 percent / 4-DMAP / pyridine / 15 h / 20 °C 2: BF3*Et2O / hexane; CH2Cl2 / 2.5 h / -20 - -15 °C View Scheme

castasterone (80736-41-0) → (1R,3aS,3bS,5R,5aS,6aS,9aR,10aR,10bS,12aS)-1-{(S)-1-[(4R,5S)-5-((S)-1,2-Dimethyl-propyl)-2,2-dimethyl-[1,3]dioxolan-4-yl]-ethyl}-8,8,10a,12a-tetramethyl-hexadecahydro-7,9-dioxa-dicyclopenta[a,h]phenanthren-5-ol

Conditions	Yield
Multi-step reaction with 2 steps 1: 77 percent / NaBH4 / methanol / 20 °C 2: 80 percent / p-toluenesulfonic acid / CH2Cl2 / 20 °C View Scheme

castasterone (80736-41-0) → (1R,3aS,3bS,5S,5aS,6aS,9aR,10aR,10bS,12aS)-1-{(S)-1-[(4R,5S)-5-((S)-1,2-Dimethyl-propyl)-2,2-dimethyl-[1,3]dioxolan-4-yl]-ethyl}-8,8,10a,12a-tetramethyl-hexadecahydro-7,9-dioxa-dicyclopenta[a,h]phenanthren-5-ol

Conditions	Yield
Multi-step reaction with 2 steps 1: 19 percent / NaBH4 / methanol / 20 °C 2: 68 percent / p-toluenesulfonic acid / CH2Cl2 / 20 °C View Scheme

castasterone (80736-41-0) → (2R,3S,5R,8S,9S,10R,13S,14S,17R)-17-((1S,2R,3R,4S)-2,3-Dihydroxy-1,4,5-trimethyl-hexyl)-10,13-dimethyl-6-methylene-hexadecahydro-cyclopenta[a]phenanthrene-2,3-diol

Conditions	Yield
Multi-step reaction with 3 steps 1: p-TsOH / CH2Cl2 / Ambient temperature 2: 79 percent / tetrahydrofuran / 2 h 3: 62 percent / aq. AcOH / tetrahydrofuran / 5 h / 70 °C View Scheme

castasterone (80736-41-0) → (1R,3aS,3bS,5aR,6aS,9aR,10aR,10bS,12aS)-1-{(S)-1-[(4R,5S)-5-((S)-1,2-Dimethyl-propyl)-2,2-dimethyl-[1,3]dioxolan-4-yl]-ethyl}-8,8,10a,12a-tetramethyl-5-methylene-hexadecahydro-7,9-dioxa-dicyclopenta[a,h]phenanthrene

Conditions	Yield
Multi-step reaction with 2 steps 1: p-TsOH / CH2Cl2 / Ambient temperature 2: 79 percent / tetrahydrofuran / 2 h View Scheme

Upstream product

• 76976-76-6 <22S,23(24)Z>-3β-tetrahydropyranyloxycholest-5,23-dien-22-ol 
• 22145-61-5 3β-(tetrahydropyran-2-yloxy)-23,24-dinorchol-5-en-22-al 
• 113599-31-8 (20R,22R)-6-(ethylenedioxy)-20,22-dihydroxy-2α,3α-(isopropylidenedioxy)-23-(methoxymethoxy)-5α-23-ergosten-28-oic acid γ-lactone 
• 113599-34-1 (20Z)-6-(ethylenedioxy)-2α,3α-(isopropylidenedioxy)-23-(methoxymethoxy)-5α-ergosta-20(22),23-dieno-28,22-lactone 
• 113599-52-3 (20R,22S,23R,24S)-20-hydroxy-2α,3α,22,23-tetracetoxy-5α-ergostan-6-one 
• 113599-54-5 (22R,23R,24S)-2α,3α,22,23-tetracetoxy-5α-ergost-20(21)-en-6-one 
• 113599-49-8 (20R,22S,23R,24R)-6-(ethylenedioxy)-20,22-dihydroxy-2α,3α-(isopropylidenedioxy)-23-(methoxymethoxy)-28-<(methylsulfonyl)oxy>-5α-ergostane 
• 113599-41-0 (22R,23R,24R)-6-(ethylenedioxy)-22-hydroxy-2α,3α-(isopropylidenedioxy)-23-(methoxymethoxy)-28-<(methylsulfonyl)oxy>-5α-ergostane 
• 113599-51-2 (20R,22S,23R,24S)-22-acetoxy-6-(ethylenedioxy)-20-hydroxy-2α,3α-(isopropylidenedioxy)-23-(methoxymethoxy)-5α-ergostane 
• 113599-44-3 (20R,22S,23R,24S)-6-(ethylenedioxy)-20-hydroxy-2α,3α-(isopropylidenedioxy)-23-(methoxymethoxy)-5α-ergostano-28,22-lactone 
• 113599-43-2 C₃₇H₆₂O₈ 
• 113599-56-7 C₃₃H₅₀O₈ 
• 113599-36-3 (22R,23R,24S)-6-(ethylenedioxy)-2α,3α-(isopropylidenedioxy)-23-(methoxymethoxy)-5α-ergostano-28,22-lactone 
• 113599-42-1 (22R,23R,24S)-6-(ethylenedioxy)-22-hydroxy-2α,3α-(isopropylidenedioxy)-23-(methoxymethoxy)-5α-ergostane 

Downstream Products

• 72962-43-7 (22R,23R,24R)-2α,3α,22,23-tetrahydro-B-homo-7-oxa-5α-ergostan-6-one 
• 72962-43-7 (22S,23S,24R)-2α,3α,22,23-tetrahydro-B-homo-7-oxa-5α-ergostan-6-one 
• 87833-54-3 6-deoxocastasterone 
• 72962-43-7 (3α,5α,6α,8β,9α,12β,13β,16α,17β)-10-[(2'α,3'β,4'β,5'β)-3,4-dihydroxy-5,6-dimethyl-2-heptanyl]-5,6-dihydroxy-7a,9a-dimethylhexadecahydro-3H-benzo[c]indeno[5,4-e]oxepin-3-one 

Relevant articles and documents

An improved synthesis of plant growth regulating steroid brassinolide and its congeners

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New Synthesis of Castasterone

An improved synthesis that could produce gram quantities of castasterone was proposed. The starting material was stigmasterol, the cyclic part of which was transformed in the first synthetic step into the 3α,5-cyclo-6-ketone. The side-chain carbon skeleton in the target compound was constructed with the required stereochemistry of the C-24 methyl via addition of methylacetylene, hydrogenation of the propargyl alcohol over Lindlar catalyst, and Claisen rearrangement. Diols were introduced using Sharpless asymmetric dihydroxylation of the intermediate ?2,22-dienone in the presence of (DHQD)2AQN. A unique feature of the synthesis was the avoidance of chromatographic separations of propargyl alcohols with similar chromatographic mobilities because the C-22 diastereomers were enriched in subsequent redox reactions.

Improved Synthesis of Castasterone and Brassinolide

Castasterone 1 is synthesized in 32% overall yield in eight steps from the known (20S)-6,6-ethylenedioxy-20-formyl-3x,5-cyclo-5x-pregnane 4.

Stereoselective Synthesis of Plant-Growth-Regulating Steroids: Brassinolide, Castasterone, and their 24,25-Substituted Analogues

Brassinosteroids and their congeners, brassinolide 1, castasterone 2, 25-methylbrassinolide 3, 25-methylcastasterone 4 and (24R)-24-phenylbrassinone 5, have been stereoselectively synthesized by employing the pyranone derivative 19 as a versatile intermediate for the construction of the side chain.