Stereochemical analysis of α1, a mating hormone of the phytopathogen Phytophthora

Ojika, Makoto; Qi, Jianhua; Kito, Yuko; Sakagami, Youji

doi:10.1016/j.tetasy.2007.07.024

Cited by 14 publications

(7 citation statements)

References 9 publications

(6 reference statements)

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“…The synthesis of the diastereomeric C3–C12 fragments (3 R ,7 R )‐ and (3 S ,7 R )‐ 7 started from commercially available ( R ) ‐ and ( S )‐butanediols 9 , but proved to be slightly more challenging than expected (Scheme ). The regioselective silylation of 9 by using tert ‐butyldiphenylsilyl chloride (TBDPSCl) in the presence of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) as a base has been reported several times,17 with regioselectivities ranging from 16:117a to 3:1 17b. In our hands, a result at the lower end of the selectivity scale was initially observed.…”

Section: Resultsmentioning

confidence: 69%

“…Aldehydes ( R )‐ and ( S )‐ 8 have also been prepared numerous times and under various oxidation conditions,17a,b,d,e, 18 but have been described as unstable 17d. The Dess–Martin oxidation was initially chosen because of its mild conditions, and it was decided to proceed with the Wittig olefination immediately after work‐up of the reaction mixture.…”

Section: Resultsmentioning

confidence: 99%

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Total Synthesis, Proof of Absolute Configuration, and Biosynthetic Origin of Stylopsal, the First Isolated Sex Pheromone of Strepsiptera

Lagoutte

Šebesta

Jiroš

et al. 2013

Chemistry A European J

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The asymmetric total synthesis of the diastereomers of stylopsal establishes the absolute configuration of the first reported sex pheromone of the twisted-wing parasite Stylops muelleri as (3R,5R,9R)-trimethyldodecanal. The key steps for the diastereo- and enantiodivergent introduction of the methyl groups are two different types of asymmetric conjugate addition reactions of organocopper reagents to α,β-unsaturated esters, whereas the dodecanal skeleton is assembled by Wittig reactions. The structure of the natural product was confirmed by chiral gas chromatography (GC) techniques, GC/MS and GC/electroantennography (EAD) as well as field tests. An investigation into the biosynthesis of the pheromone revealed that it is likely to be produced by decarboxylation of a 4,6,10-trimethyltridecanoic acid derivative, which was found in substantial amounts in the fat body of the female, but not in the host bee Andrena vaga. This triple-branched fatty acid precursor thus seems to be biosynthesized de novo through a polyketide pathway with two consecutive propionate-propionate-acetate assemblies to form the complete skeleton. The simplified, motionless and fully host-dependent female exploits a remarkable strategy to maximize its reproductive success by employing a relatively complex and potent sex pheromone.

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Section: Resultsmentioning

confidence: 69%

Section: Resultsmentioning

confidence: 99%

Total Synthesis, Proof of Absolute Configuration, and Biosynthetic Origin of Stylopsal, the First Isolated Sex Pheromone of Strepsiptera

Lagoutte

Šebesta

Jiroš

et al. 2013

Chemistry A European J

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“…91) The C15 configuration was deduced to be (R) and the C3 configuration to be a 3:2 mixture of (R) and (S), which reduced the number of possible diastereomers to four. 92) Qin's group developed a chiral synthon approach to the asymmetric synthesis of 1 (Scheme 6 [3]). 93) The addition of 65 to lithium salts of 66 generated by tin/ lithium exchange yielded 67.…”

Section: Synthesis Of Phytophthora Mating Hormonementioning

confidence: 99%

Synthesis of Microbial Signaling Molecules and Their Stereochemistry-Activity Relationships

Yajima

2011

Bioscience, Biotechnology, and Biochemistry

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Microbial signaling molecules such as autoinducers and microbial hormones play important roles in intercellular communication in microorganisms. Information transfer between the individual cells of a microorganism is one of the most important biological events among them. Researchers often suffer from extremely low levels of microbial signaling molecule contents, which prevent them from understanding chemistry and biology of intercellular communication in microorganisms. Chemical synthesis is a powerful tool to obtain sufficient amounts of sample and to clarify the structure of a molecule. This review focuses on the synthesis and stereochemistry-bioactivity relationships of five microbial signaling molecules, Vibrio cholerae autoinducer-1 (CAI-1), AI-2 precursor (DPD), an acylhomoserine lactone from Rhizobium leguminosarum (small bacteriocin), a diffusible extracellular factor of Xanthomondas campestris pv. campestris, and Phytophthora mating hormone α1.

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“…[3] Yajima et al reported the first asymmetric synthesis of a stereoisomer library of a 1 and concluded that the absolute configuration was (3R, 7R, 11R, 15R) based upon oosporeinducing assays. [4] A number of total syntheses of 1 have since been reported, [5] but in particular, the detailed and thorough analysis of all stereoisomers of 1 by Bajpai and Curran [6] is especially noteworthy.…”

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confidence: 99%

Short Stereoselective Synthesis of the Phytophthora Universal Mating Hormone α1 Using Lithiation/Borylation Reactions

2014

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The universal mating hormone a 1 of the virulent plant pathogen Phytophthora has been synthesized in 12 steps and 28 % overall yield. Key CÀC bond-forming steps involved the use of two lithiation/borylation reactions to couple together enantioenriched building blocks, one of which also set up the stereochemistry of the tertiary alcohol at C11. Detailed analysis showed that the diastereomeric purity of the target molecule was > 91 %, the highest obtained to date.

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Stereochemical analysis of α1, a mating hormone of the phytopathogen Phytophthora

Cited by 14 publications

References 9 publications

Total Synthesis, Proof of Absolute Configuration, and Biosynthetic Origin of Stylopsal, the First Isolated Sex Pheromone of Strepsiptera

Total Synthesis, Proof of Absolute Configuration, and Biosynthetic Origin of Stylopsal, the First Isolated Sex Pheromone of Strepsiptera

Synthesis of Microbial Signaling Molecules and Their Stereochemistry-Activity Relationships

Short Stereoselective Synthesis of the Phytophthora Universal Mating Hormone α1 Using Lithiation/Borylation Reactions

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