34582-29-1

Upstream product

• 1010-99-7 3-(tert-butyl)-5-methylbenzene-1,2-diol 
• 77-78-1 dimethyl sulfate 
• 203984-66-1 2-bromo-5-(tert-butyl)-3,4-dimethoxy-1-methylbenzene 
• 333401-63-1 5-tert-butyl-3,4-dimethoxybenzaldehyde 
• 2505-15-9 6-(tert-butyl)-2-methoxy-4-methylphenol 
• 74-88-4 methyl iodide 

Downstream Products

• 203984-66-1 2-bromo-5-(tert-butyl)-3,4-dimethoxy-1-methylbenzene 
• 333401-61-9 5-bromomethyl-3-tert-butyl-1,2-dimethoxybenzene 
• 203984-68-3 2-Bromo-5-tert-butyl-3,4-dimethoxy-benzoic acid 3-tert-butyl-2-methoxy-5-methyl-phenyl ester 
• 203984-67-2 2-bromo-5-tert-butyl-3,4-dimethoxybenzoic acid 
• 333401-64-2 (rac)-4,5'-di-tert-butyl-6-methyl-2,3,3',4'-tetramethoxy-diphenylmethanol 
• 333401-66-4 4,5'-di-tert-butyl-6-methyl-2,3,3',4'-tetramethoxy-diphenylmethane 
• 333401-65-3 1,2-bis(5'-tert-butyl-3',4'-dimethoxyphenyl)ethane 
• 333401-62-0 5-tert-butyl-3,4-dimethoxybenzyl alcohol 
• 333401-63-1 5-tert-butyl-3,4-dimethoxybenzaldehyde 

Relevant academic research and scientific papers

Palladium-Catalyzed, tert-Butyllithium-Mediated Dimerization of Aryl Halides and Its Application in the Atropselective Total Synthesis of Mastigophorene A

A palladium-catalyzed direct synthesis of symmetric biaryl compounds from aryl halides in the presence of tBuLi is described. In situ lithium-halogen exchange generates the corresponding aryl lithium reagent, which undergoes a homocoupling reaction with a second molecule of the aryl halide in the presence of the palladium catalyst (1 mol %). The reaction takes place at room temperature, is fast (1 h), and affords the corresponding biaryl compounds in good to excellent yields. The application of the method is demonstrated in an efficient asymmetric total synthesis of mastigophorene A. The chiral biaryl axis is constructed with an atropselectivity of 9:1 owing to catalyst-induced remote point-to-axial chirality transfer. It takes two: A palladium-catalyzed direct homocoupling of aryl halides in the presence of tBuLi enabled the synthesis of even tetra-ortho-substituted symmetric biaryl compounds in high yield (see scheme). The method was applied to the asymmetric synthesis of mastigophorene A in just eight steps through straightforward enantioselective installation of the benzylic quaternary stereocenter and highly diastereoselective homocoupling.

First total synthesis of the mastigophorenes C and D and of simplified unnatural analogs

The first total synthesis of the mastigophorenes C (2) and D (3), natural 'dimeric' sesquiterpenes isolated from the liverwort Mastigophora diclados with interesting biological activities, is described. As previously for mastigophorenes A (1) and B, the divergent synthetic approach was first optimized on a simplified model system with a tert-butyl group instead of the chiral cyclopentyl residue, also in order to find more easily available compounds with similar or even improved biological activity.

Atropo-anantioselective synthesis of a simplified analog of mastigophorenes A and B

A first approach to the atroposelective total synthesis of mastigophorenes is described, the directed preparation of a structurally slightly modified analog of mastigophorenes A and B, with a tert-butyl instead of a substituted, chiral cyclopentyl residue. Its (partially protected) monomeric half is dimerized by oxidative (phenolic) coupling to give the corresponding biphenyl in a racemic form, or atropo-enantioselectively via the corresponding biaryl lactone, to give the M- or, optionally, the P-enantiomeric form, by stereoselective ring opening and subsequent standard transformations.