Asymmetric Syntheses of the Sex Pheromones of Pine Sawflies, Their Homologs and Stereoisomers

Zheng, Jian‐Feng; Lan, Hong-Qiao; Yang, Ruining; Peng, Qi-Long; Xiao, Zhen-Hua; Tuo, Shi‐Chuan; Hu, Kong-Zhen; Xiang, Yonggang; Wei, Zhen; Zhang, Zhen; Huang, Pei‐Qiang

doi:10.1002/hlca.201200341

Cited by 5 publications

(1 citation statement)

References 53 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…56 Malic acid (S10), which has no methyl groups but a secondary hydroxyl group, was concisely employed for the synthesis of the C 15 3,7-dimethyl 2-acetoxy pheromone (56) containing three stereogenic centres. 176,178 Tosylation and LiAlH 4 reduction of the dimethyl ester of (S)-S10 produced a C 4 diol with an inverted conguration, and its secondary tosylate was coupled with a Grignard reagent to make a C 11 monomethyl moiety with an S conguration associated stereoselective inversion again. Another C 4 moiety with a 2S,3S conguration was also made from (S)-S10 by stereoselective methylation using LiHMDS as a base and LiAlH 4 reduction as a key reaction, and then linked with the C 11 moiety to yield (2S,3S,7S)-56.…”

Section: Employment Of Chiral Sourcesmentioning

confidence: 99%

Chiral methyl-branched pheromones

Ando

Yamakawa

2015

Nat. Prod. Rep.

View full text Add to dashboard Cite

Insect pheromones are some of the most interesting natural products because they are utilized for interspecific communication between various insects, such as beetles, moths, ants, and cockroaches. A large number of compounds of many kinds have been identified as pheromone components, reflecting the diversity of insect species. While this review deals only with chiral methyl-branched pheromones, the chemical structures of more than one hundred non-terpene compounds have been determined by applying excellent analytical techniques. Furthermore, their stereoselective syntheses have been achieved by employing trustworthy chiral sources and ingenious enantioselective reactions. The information has been reviewed here not only to make them available for new research but also to understand the characteristic chemical structures of the chiral pheromones. Since biosynthetic studies are still limited, it might be meaningful to examine whether the structures, particularly the positions and configurations of the branched methyl groups, are correlated with the taxonomy of the pheromone producers and also with the function of the pheromones in communication systems.

show abstract

Section: Employment Of Chiral Sourcesmentioning

confidence: 99%

Chiral methyl-branched pheromones

Ando

Yamakawa

2015

Nat. Prod. Rep.

View full text Add to dashboard Cite

show abstract

Bio‐inspired Step‐Economical, Redox‐Economical and Protecting‐Group‐Free Enantioselective Total Syntheses of (−)‐Chaetominine and Analogues

Luo¹,

Peng²,

Xu³

et al. 2014

Chin. J. Chem.

View full text Add to dashboard Cite

Full details of the enantioselective four‐step and five‐step total syntheses of (−)‐chaetominine from D‐Trp and L‐Trp are described. Featuring an oxidative double cyclization reaction, and tandem C14 epimerization‐lactamization reactions as key steps, the method provides a rapid access to (−)‐chaetominine (6a) and analogues. The total syntheses of (−)‐chaetominine (6a) are so far the most concise and efficient. Through comprehensive investigation, the stereochemical requirements for the double cyclization reaction were revealed, and the confusion regarding physicochemical properties of this natural product was clarified. Moreover, short pathways to complexity generation, a scenarios revealed for the biosynthesis of fungal peptidyl alkaloid multi‐cyclic scaffolds, have been validated through the chemical synthesis. On the basis of these findings, a plausible biosynthetic pathway for (−)‐chaetominine (6a) was suggested.

show abstract

Towards Reaction Control: An Expeditious Access to Racemic 5‐Substituted Tetramates and 5‐Substituted Tetramic Acids from Malimides

Huang

2014

Chin. J. Chem.

Self Cite

View full text Add to dashboard Cite

A versatile and divergent two-step transformation of malimides to racemic tetramates and tetramic acids is described. The method consists of Grignard reagent addition with malimides to give hemiaminals and concentrated HCl-promoted chemoselective transformations of the latter. When running the reaction in CH 2 Cl 2 and in the presence of 2.5 molar equiv. of conc. HCl, 5-alkyltetramates were formed, while in neat conc. HCl, 5-alkyltetramic acids were obtained. Using this method, a variety of title compounds were prepared in good to excellent yields (82% -99%, and 76%/85%). The work also constitutes a formal racemic total synthesis of reutericyclin. On the basis of the experimental evidences and of a deuterium labeling experiment, a plausible reaction mechanism was proposed. This work thus demonstrated two new types of step economical and chemodivergent transformations starting from malic acid.

show abstract

Asymmetric Syntheses of the Sex Pheromones of Pine Sawflies, Their Homologs and Stereoisomers

Cited by 5 publications

References 53 publications

Chiral methyl-branched pheromones

Chiral methyl-branched pheromones

Bio‐inspired Step‐Economical, Redox‐Economical and Protecting‐Group‐Free Enantioselective Total Syntheses of (−)‐Chaetominine and Analogues

Towards Reaction Control: An Expeditious Access to Racemic 5‐Substituted Tetramates and 5‐Substituted Tetramic Acids from Malimides

Contact Info

Product

Resources

About