Stereospecific synthesis of <i>S</i>-(−)-<i>trans</i>-verbenol and its antipode by inversion of sterically hindered alcohols

Liu, Fu; Fang, Jiaxing; Kong, Xiangbo; Zhang, Sufang; Zhang, Zhen

doi:10.1080/10286020.2020.1839433

Cited by 4 publications

(1 citation statement)

References 14 publications

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“…Thus, we need to invert the stereochemistry of the resulting secondary alcohol to obtain the desired natural product. To this end, mesylation of 22 followed a H 2 O-mediated S N 2 reaction was implemented, which led to the desired product 7 in a yield of 20% . Interestingly, we found that a substantial amount of 6 (40%) could also be isolated in the reaction, which should be derived from 22 through a S N 2′ reaction.…”

Section: Resultsmentioning

confidence: 96%

Chiral Bisphosphine-Catalyzed Asymmetric Staudinger/aza-Wittig Reaction: An Enantioselective Desymmetrizing Approach to Crinine-Type Amaryllidaceae Alkaloids

Yang,

Zhang,

Zhang

et al. 2024

J. Am. Chem. Soc.

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An unprecedented chiral bisphosphine-catalyzed asymmetric Staudinger/aza-Wittig reaction of 2,2-disubstituted cyclohexane-1,3-diones is reported, enabling the facile access of a broad range of cis-3a-arylhydroindoles in high yields with excellent enantioselectivities. The key to the success of this work relies on the first application of chiral bisphosphine DuanPhos to the asymmetric Staudinger/aza-Wittig reaction. An effective reductive system has been established to address the challenging P V �O/P III redox cycle associated with the chiral bisphosphine catalyst. In addition, comprehensive experimental and computational investigations were carried out to elucidate the mechanism of the asymmetric reaction. Leveraging the newly developed chemistry, the enantioselective total syntheses of several crinine-type Amaryllidaceae alkaloids, including (+)-powelline, (+)-buphanamine, (+)-vittatine, and (+)-crinane, have been accomplished with remarkable conciseness and efficiency.

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Section: Resultsmentioning

confidence: 96%

Chiral Bisphosphine-Catalyzed Asymmetric Staudinger/aza-Wittig Reaction: An Enantioselective Desymmetrizing Approach to Crinine-Type Amaryllidaceae Alkaloids

Yang,

Zhang,

Zhang

et al. 2024

J. Am. Chem. Soc.

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Divergent Response of Two Bark Beetle–Fungal Symbiotic Systems to Host Monoterpenes Reflects Niche Partitioning Strategies

Bai,

Fang,

et al. 2024

J Chem Ecol

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Monoterpenoid signals and their transcriptional responses to feeding and juvenile hormone regulation in bark beetle Ips hauser i

Fang

Shi

et al. 2021

Journal of Experimental Biology

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Hauser's engraver beetle, Ips hauseri, is a serious pest in spruce forest ecosystems in Central Asia. Its monoterpenoid signal production, transcriptome responses and potential regulatory mechanisms remain poorly understood. The quality and quantity of volatile metabolites in hindgut extracts of I. hauseri were found to differ between males and females and among three groups: beetles that were newly emerged, those with a topical application of juvenile hormone III (JHIII) and those that had been feeding for 24 h. Feeding males definitively dominated monoterpenoid signal production in I. hauseri, which uses (4S)-(−)-ipsenol and (S)-(−)-cis-verbenol to implement reproductive segregation from Ipstypographus and Ipsshangrila. Feeding stimulation induced higher expression of most genes related to the biosynthesis of (4S)-(−)-ipsenol than JHIII induction, and showed a male-specific mode in I. hauseri. JHIII stimulated males to produce large amounts of (−)-verbenone and also upregulated the expression of several CYP6 genes, to a greater extent in males than in females. The expression of genes involved in the metabolism of JHIII in females and males was also found to be upregulated. Our results indicate that a species-specific aggregation pheromone system for I. hauseri, consisting of (4S)-(−)-ipsenol and S-(−)-cis-verbenol, can be used to monitor population dynamics or mass trap killing. Our results also enable a better understanding of the bottom-up role of feeding behaviors in mediating population reproduction/aggregation and interspecific interactions.

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Stereospecific synthesis of S-(−)-trans-verbenol and its antipode by inversion of sterically hindered alcohols

Cited by 4 publications

References 14 publications

Chiral Bisphosphine-Catalyzed Asymmetric Staudinger/aza-Wittig Reaction: An Enantioselective Desymmetrizing Approach to Crinine-Type Amaryllidaceae Alkaloids

Chiral Bisphosphine-Catalyzed Asymmetric Staudinger/aza-Wittig Reaction: An Enantioselective Desymmetrizing Approach to Crinine-Type Amaryllidaceae Alkaloids

Divergent Response of Two Bark Beetle–Fungal Symbiotic Systems to Host Monoterpenes Reflects Niche Partitioning Strategies

Monoterpenoid signals and their transcriptional responses to feeding and juvenile hormone regulation in bark beetle Ips hauser i

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