Refernces
10.1016/S0040-4039(00)98306-0
The research focuses on the total synthesis of verticillene (2), which is considered the biogenetic precursor of the taxane family of alkaloids. The purpose of the study was to develop a synthesis method for E,E-verticillene (2), a compound derived from geranyl-geranyl pyrophosphate and related to other constituents of conifer wood. The researchers achieved this through an intramolecular reductive coupling of bis-aldehyde (14) in the presence of titanium(0), followed by a 1,4-reduction of the resulting tetraene (16) using sodium in ammonia. Key chemicals used in the process included 3-isobutoxycyclohexenone, E-3,7-dimethylocta-2,6-dienyl bromide, lithium dimethylcuprate, chlorotrimethylsilane, titanium tetrachloride, methylmagnesium iodide, phosphorus oxychloride, and potassium hydroxide, among others. The conclusion of the study was the successful synthesis of E,E-verticillene (2), confirmed by comparing its spectral data with that of natural verticillol (1), thus validating the proposed biosynthetic pathway.
10.1055/s-0028-1087672
The research focuses on the development of a flexible and highly regio- and diastereoselective approach to synthesize methyl 5-alkyltetramate derivatives, which are key frameworks in numerous bioactive natural products. The method involves regioselective Grignard reagent additions to 3-methoxymaleimides, followed by diastereoselective reductive dehydroxylation of the resulting N,O-acetals. The experiments utilized various Grignard reagents, such as methyl magnesium iodide and n-butyllithium, and reagents like boron trifluoride etherate and triethylsilane for the reductive dehydroxylation step. The study also explored the use of (S)-phenylglycinol as a chiral auxiliary in the synthesis. The analyses included monitoring the reactions, determining the yields and diastereoselectivities of the products, and characterizing the structures of the synthesized compounds using techniques like X-ray diffraction analysis for compound 29h. The research resulted in the synthesis of various methyl (5S)-5-alkyltetramate derivatives that are otherwise inaccessible by conventional methods based on α-amino acids.
10.1016/S0008-6215(00)80685-0
The research investigates the stereoselectivities in the reactions of diazomethane with various α-D-hexopyranosid-4-uloses and compares them with those in Grignard reactions. The study synthesizes several new α-D-hexopyranosid-4-uloses, including compounds 1, 3, 4, 5, and 6, using methods such as N-bromosuccinimide reactions, sodium borohydride reduction, and benzylation. The nucleophilic reactions of these compounds with diazomethane and Grignard reagents, specifically methylmagnesium iodide, are examined. The configurations of the resulting spiro-epoxides and other products are determined using 1H-NMR and 13C-NMR spectroscopy. The results support the hypothesis that the stereoselectivity of the diazomethane reaction is mainly controlled by the attractive, electrostatic force between the diazomethyl cation and neighboring axial oxygen atoms or the axial lone-pair electrons of O-5 in the transition state. Key chemicals involved in the research include diazomethane, methylmagnesium iodide, α-D-hexopyranosid-4-uloses, N-bromosuccinimide, sodium borohydride, and various derivatives of these compounds.
10.1021/jo01225a005
The study focuses on the synthesis and analysis of certain benzanthracene derivatives with potential estrogenic and carcinogenic properties. The researchers synthesized various 9,10-dialkyl-9,10-dihydroxy-9,10-dihydro-1,2-benzanthracenes and related compounds, starting from 1,2-benzanthraquinone and 5-phenyl-1,2-benzanthraquinone. They used Grignard reagents, such as methylmagnesium iodide, ethylmagnesium bromide, and n-propylmagnesium bromide, to introduce different alkyl groups into the benzanthracene structure. The synthesized compounds were then tested for their ability to induce oestrus in ovarietomized mice, revealing that some of them, particularly those with ethyl and n-propyl groups, exhibited significant estrogenic activity. Additionally, the study explored the relationship between chemical structure and both estrogenic and carcinogenic properties, aiming to understand how modifications to the benzanthracene core affect these biological activities.