142632-32-4

Basic information

• Product Name: CALANOLIDE A
• Synonyms: CALANOLIDE A;(+)-(10R,11S,12S)-12-HYDROXY-6,6,10,11-TETRAMETHYL-4-PROPYL-11,12-DIHYDRO-2H,6H,10H-BENZO(1,2-B:3,4-B':5,6-B'']TRIPYRAN-2-ONE;CALANOLIDE A,(+)-(10R,11S，12S)-12-HYDROXY-6,6,10,11-TETRAMETHYL-4-PROPYL-11，12-DIHYDRO-2H，6H,10H-BENZO(1，2-B：3,4-B'：5,6-B ]TRIPYRAN-2-ONE;(10R,11S,12S)-12-hydroxy-6,6,10,11-tetramethyl-4-propyl-11,12-dihydro-2H,6H,10H-dipyrano[2,3-f:2',3'-h]chromen-2-one
• CAS NO: 142632-32-4
• Molecular Formula: C22H26O5
• Molecular Weight: 370.44
• Mol File: 142632-32-4.mol

Chemical Properties

• Boiling Point: 514.8°Cat760mmHg
• Flash Point: 177.2°C
• Appearance: /
• Density: 1.181g/cm³
• Vapor Pressure: 2E-11mmHg at 25°C
• Refractive Index: 1.558
• CAS DataBase Reference: CALANOLIDE A(CAS DataBase Reference)
• NIST Chemistry Reference: CALANOLIDE A(142632-32-4)
• EPA Substance Registry System: CALANOLIDE A(142632-32-4)

Safety Data

• Hazardous Substances Data: 142632-32-4(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Industry:
CALANOLIDE A is used as an experimental non-nucleoside reverse transcriptase inhibitor for its potent anti-HIV activity. CALANOLIDE A has shown promise in inhibiting the replication of the HIV virus, making it a valuable asset in the development of new treatments and therapies for HIV-infected individuals.

InChI:InChI=1/C22H26O5/c1-6-7-13-10-15(23)26-21-16(13)20-14(8-9-22(4,5)27-20)19-17(21)18(24)11(2)12(3)25-19/h8-12,18,24H,6-7H2,1-5H3/t11?,12-,18+/m1/s1

Upstream product

• 161753-49-7 (+/-)-12-oxocalanolide A 
• 183904-55-4 HI-D₈₆ 
• 107-86-8 3,3-dimethyl acrylaldehyde 
• 685844-44-4 5-hydroxy-8,9-dimethyl-4-propyl-8,9-dihydro-pyrano[2,3-f]chromene-2,10-dione 
• 334881-61-7 (8R,9S)-8,9-dihydro-8,9-dimethyl-5-methoxy-4-propyl-2H,10H-benzo[1,2-b;5,6-b']dipyran-2,10-dione 
• 263351-94-6 (10R,11S)-10,11-dihydro-4-propyl-6,6,10,11-tetramethyl-2H,6H,12H-benzo[1,2-b;3,4-b';5,6-b'']tripyran-2,12-dione 
• 166983-61-5 HI-D₁₂ 
• 185339-26-8 5-Hydroxy-6-((2R,3S)-3-hydroxy-2-methyl-butyryl)-2,2-dimethyl-10-propyl-2H-pyrano[2,3-f]chromen-8-one 
• 185339-28-0 5-Hydroxy-6-((2R,3R)-3-hydroxy-2-methyl-butyryl)-2,2-dimethyl-10-propyl-2H-pyrano[2,3-f]chromen-8-one 
• 108-73-6 3,5-dihydroxyphenol 
• 31525-67-4 dimethylacetal of 3-methyl-3-hydroxybutyraldehyde 
• 66346-59-6 5,7-dihydroxy-4-propylcoumarin 
• 3249-68-1 ethyl butyroyl acetate 
• 166983-58-0 5,7-Dihydroxy-8-propanoyl-4-propyl-2H-1-benzopyran-2-one 

Relevant articles and documents

Synthesis of (+)-calanolide A, an anti-HIV agent, via enzyme-catalyzed resolution of the aldol products

The synthesis of (+)-calanolide A (1), an anti-HIV-1 agent, is described. A TiCl4-mediated aldol reaction of compound 2 stereoselectively produced the desired syn diastereomer (±)-5, which was resolved by a lipase-catalyzed acylation reaction. Under Mitsunobu conditions (Ph3P/DEAD), the syn aldol product (+)-5 led to the formation of trans-2,3-dimethyl chroman-4-one [(+)-3] with 94% ee, while the anti aldol product (+)-6 yielded both trans and cis derivatives (+)-3 and (+)-4 with 60% and 68% ee, respectively. Luche reduction on (+)-3 led to (+)-1 and (+)-calanolide B in a ratio of 9:1. Copyright (C) Elsevier Science Ltd.

Synthesis, chromatographic resolution, and anti-human immunodeficiency virus activity of (±)-calanolide A and its enantiomers

The anti-HIV agent (±)-calanolide A (1) has been synthesized in a five- step approach starting with phloroglucinol [→ 5 → 6 → 11 → 18 → (±)- 1], which includes Pechmann reaction, Friedel-Crafts acylation, chromenylation with 4,4-dimethoxy-2-methylbutan-2-ol, cyclization, and Luche reduction. Cyclization of chromene 11 to chromanone 18 was achieved by employing either acetaldehyde diethyl acetal or paraldehyde in the presence of trifluoroacetic acid and pyridine or PPTS. Luche reduction of chromanone 18 at lower temperature preferably yielded (±)-1. Reduction of chromone 12, synthesized by Kostanecki-Robinson reaction from chromene 11, failed to afford (±)-1. The synthetic (±)-1 has been chromatographically resolved into its optically active forms, (+)- and (-)-1. The anti-HIV activities for synthetic (±)-1, as well as resultant (+)- and (-)-1, have been determined. Only (+)-1 accounted for anti-HIV activity, which was similar to the data reported for the natural product, and (-)-1 was inactive.

Chemical resolution of (±)-calanolide A, (±)-cordatolide A and their 11-demethyl analogues

The chemical resolution of (±)-calanolide A and (±)-cordatolide A into their corresponding optically active enantiomers is described. Their inhibitory activities against HIV-1 are tested in vitro.

Concise Synthesis of Anti-HIV-1 Active (+)-Inophyllum B and (+)-Calanolide A by Application of (-)-Quinine-Catalyzed Intramolecular Oxo-Michael Addition

(-)-Quinine-catalyzed intramolecular oxo-Michael addition (IMA) of 7-hydroxy-5-methoxy-8-tigloylcoumarins was developed for the enantioselective construction of 2,3-dimethyl-4-chromanone systems in the context of the asymmetric synthesis of anti-HIV-1 act

PROCESSES FOR PREPARING CALANOLIDE A AND INTERMEDIATES THEREOF

The present invention provides a production method of Calanolide A according to the following method wherein each symbol is as defined in the specification, as a more convenient and industrially practical method for the synthesis of Calanolide A from an easily available starting material.

Methods for preparing antiviral calanolide compounds

The present invention relates to methods for preparing 2,2-dimethyl-5-acyloxy-10-propyl-2H,8H-benzo[ 1,2-b:3,4-b ′]dipyran-8-one (5) and 2,2-dimethyl-5-hydroxy- 10-propyl-2H,8H-benzo[1,2-b:3,4-b ′]dipyran-8-one (6) and their use as intermediates for the synthesis of antiviral calanolide compounds. For example, Fries rearrangement on compound 5 or Friedel-Crafts reaction on 6, yields intermediate 2,2-dimethyl-5-hydroxy-6-propionyl-10-propyl-2H,8H-benzo[1,2-b:3,4-b′]dipyran-8-one (4), which, in turn, can be converted to (+)-calanolide A and (?)-calanolide B. The coupling of compound 6 with the appropriate chiral molecule under Mitsunobu or nucleophilic displacement leads to the asymmetric synthesis of antiviral calanolide compounds.

Method for treating and preventing mycobacterium infections

Calanolides and analogues thereof that demonstrate potent mycobacterium activity are provided. Also provided is a method of using calanolides and analogues thereof for treating or preventing mycobacterium infections. The calanolides and analogues thereof provided are obtained via syntheses employing chromene 4 and chromanone 7 as key intermediates.

Enantioselective total synthesis of anti HIV-1 active (+)-calanolide A through a quinine-catalyzed asymmetric intramolecular oxo-Michael addition

Enantioselective total synthesis of anti HIV-1 active (+)-calanolide A was achieved by a quinine-catalyzed asymmetric intramolecular oxo-Michael addition as a key step. (C) 2000 Elsevier Science Ltd.

Method for the preparation of (+/-)-calanolide A and intermediates thereof

A method of preparing (+/-)-calanolide A, 1, a potent HIV reverse transcriptase inhibitor, from chromene 4 is provided. Useful intermediates for preparing (+/-)-calanolide A and its derivatives are also provided. According to the disclosed method, chromene 4 intermediate was reacted with acetaldehyde diethyl acetal or paraldehyde in the presence of an acid catalyst with heating, or a two-step reaction including an aldol reaction with acetaldehyde and cyclization either under acidic conditions or neutral Mitsunobu conditions, to produce chromanone 7. Reduction of chromanone 7 with sodium borohydride, in the presence of cerium trichloride, produced (+/-)-calanolide A. A method for resolving (+/-)-calanolide A into its optically active forms by a chiral HPLC system or by enzymatic acylation and hydrolysis is also disclosed. Finally, a method for treating or preventing a viral infections using (+/-)-calanolide or (-)-calanolide is provided.

Method for the preparation of (+)-calanolide a and analogues thereof

A method of preparing (+)-calanolide A, 1, a potent HIV reverse transcriptase inhibitor, from chromene 4 is provided. According to the disclosed method, chromene 4 intermediate was subjected to a chlorotitanium-mediated aldol reaction with acetaldehyde to selectively produce (±)-8a. Separation and enzyme-mediated resolution of (±)-8a produced (+)-8a. Cyclization of (+)-8a under neutral Mitsunobu conditions followed by Luche reduction of (+)-7 produced (+)-calanolide A in high yield and enantiomeric purity. The method of the invention has been extended to produce potent antiviral calanolide A analogues.