2074-29-5

Upstream product

• 2074-29-5 gibberellin A₄ methyl ester 
• 186581-53-3 diazomethane 
• 468-44-0 Gibberellin A₄ 
• 75884-80-9 methyl 3-didehydrogibberellin A₇ 
• 198990-73-7 ent-3α-acetoxy-10β-hydroxy-13-iodo-20-norgibberell-16-ene-7,19-dioic acid 7-methyl ester 19,10-lactone 
• 55732-63-3 ent-3α-acetoxy-13-hydroxy-gibberella-1,16-dien-7-oic acid 7-mehyl ester 19,10-lactone 
• 151670-90-5 ent-3α-acetoxy-10β-hydroxy-13-methylsulfonyloxy-20-norgibberell-16-ene-7,19-dioic acid 7-methyl ester 19,10-lactone 
• 53399-75-0 2β-acetoxy-4a,7-dihydroxy-1β-methyl-8-methylene-4aα,7β-gibbane-1α,10β-dicarboxylic acid-1=>4a lactone-10-methyl ester 
• 510-50-9 gibberellic acid methyl ester 
• 75884-80-9 ent-10β-hydroxy-3-oxo-20-norgibberell-1,16-diene-7,19-dioic acid 7-methyl ester 19,10-lactone 
• 75885-06-2 C₂₇H₃₀O₅S 

Downstream Products

• 2074-29-5 3-epi-gibberellin A₄ methyl ester 
• 19124-90-4 gibberellin A₄ methyl ester 
• 427-77-0 Gibberellin-A⁽⁹⁾ 
• 2112-08-5 gibberellin A₉ methyl ester 
• 2112-08-5 gibberellin A₉ 7-methyl ester 
• 75885-06-2 C₂₇H₃₀O₅S 

Relevant academic research and scientific papers

A New Method for the Deoxygenation of Tertiary and Secondary Alcohols

The derivatisation of alcohols as their methyl oxalyl esters is shown to be a convenient and selective method for deoxygenation by stannyl radicals.

Displacement of bridgehead sulfonate esters with organometallic reagents: Synthesis of 13-alkylated gibberellins

Gibberellin A3 is converted to 13-methyl GA4 in nine steps and 58% overall yield. A key step in the synthesis is the substitution of a bridgehead sulfonate ester by an alkyl group. A series of organometallic reagents have been investigated to effect this transformation; optimal yields are obtained from reaction of a methanesulfonate with a Gilman-type organocuprate in diethyl ether, in the presence of boron trifluoride-diethyl ether, thus enabling a variety of bridgehead substituents to be introduced in good to excellent yield.

Isolation and stereocontrolled synthesis of a 17-hydroxy-16β, 17-dihydrogibberellin, GA82

A 17-hydroxy-16β, 17-dihydrogibberellin, GA829, was first isolated from a fungus, Phaeosphaeria sp. L487, and was synthesized from naturally abundant GA41 in a highly stereocontrolled manner whose essential step was inversion of C(16) configuration of readily accessible 16β-formyl intermediate 5 to more stable 16α-epimer 6 by base treatment.

3-EPI-GA63, ANTHERIDIOGEN IN ANEMIA PHYLLITIDIS

3-Epi-Gibberellin A63 (3-epi-GA63) was identified by full-scan GC-mass spectrometry of a purified extract from culture media of prothallia of the fern, Anemia phyllitidis.This is the third antheriodiogen, following antheridic acid and 3α-hydroxy-9,15-cyclo-GA9, in this species. 3-Epi-GA63 showed slightly less activity than antheridic acid in antheridial formation and dark spore germination assays. - Key words: Anemia phyllitidis; Schizaeaceae; fern; prothallia; antheridiogen; antheridic acid; 3-epi-gibberellin A63.

N.m.r. Assignements of Ring A Hydrogens in Gibberellin A4 Methyl Esters and some Derivatives

Full assignements of the 1H n.m.r. chemical shifts of the ring A protons in gibberellin A4, 3-epi-gibberellin A4 and 3-oxogibberellin A4 methyl esters have been made on the basis of 1H and 2H n.m.r. data of -, -, and -labelled derivatives.These assignements have been used to determine the stereochemistry of the deuterium atoms in gibberellin A4 methyl ester, prepared via catalytic deuteriogenation of gibberellin A7 16,17-epoxide methyl ester.

Partial Synthesis of Gibberellin A9 and Gibberellin A9; Gibberellin A5 and Gibberellin A5; and Gibberellin A20 and Gibberellin A20

The 3α-alcohols, obtained by reduction of 3-didehydrogibberellin A3 methyl ester 13-acetate with lithium borohydride, borodeuteride, and borotritiide, have been converted into the 3β-chloro-derivatives and, hence, by reduction with tri-n-butylstannane followed by hydrolysis, into gibberellin A20, gibberellin A20, and gibberellin A20. Gibberellin A20 has been prepared from the product of the reduction of the 3-thiobenzoate of the 3α-alcohol with tri-n-butylstannane.The 3β-alcohols, minor products of these reductions, have been dehydrated and hydrolysed to give gibberellin A5 and gibberellin A5.The 3α-alcohol, from the lithium borohydride reduction of 3-didehydrogibberellin A7 has been transformed into the 3β-chloro-derivative and the 3-thiobenzoate which, with tri-n-butylstannane, or with tri-n-butylstannane, followed by hydrolysis, yielded gibberellin A9, gibberellin A9, or gibberellin A9.In an analogous way, the product of reduction of 3-didehydrogibberellin A4 with lithium borodeuteride was converted into gibberellin A9.The mass spectral fragmentation of the methyl esters and methyl ester trimethylsilyl ethers of gibberellins are also discussed.

Mechanism and Stereochemistry of Conjugate Reduction of Enones from Gibberellins A3 and A7

Conjugate reduction of the methyl esters of 3-didehydrogibberellin A3 13-acetate and of 3-didehydrogibberellin A7, in aprotic solvents by borohydride (or borodeuteride), is shown to introduce hydrogen (or deuterium) at the 1β- and 3β-positions in the products, 3-epi-gibberellin A1 13-acetate and 3-epi-gibberellin A4 methyl esters.The third hydrogen (or deuterium) comes from the proton (or deuteron) source used in the work-up.A mechanism for conjugate reduction of enones is proposed.The products from the borodeuteride reduction of 3-didehydrogibberellin A7 methyl ester with proton and deuteron work-up were chemically converted into -, -, and -gibberellin A4 and the stereochemistries of the deuterium atoms were determined from the deuterium content of the metabolites, formed from these labelled gibberellins in cultures of Gibberella fujikuroi, mutant B1-41a.