496789-47-0

Upstream product

• 496789-44-7 (S)-3-(3-{3-[2-((S)-1-Amino-2-methyl-propyl)-4-benzyloxymethyl-oxazol-5-yl]-7-bromo-2-oxo-2,3-dihydro-1H-indol-3-yl}-4-hydroxy-phenyl)-2-benzyloxycarbonylamino-propionic acid methyl ester 
• 496789-45-8 2-benzyloxycarbonylamino-3-(3-{3-[4-benzyloxymethyl-2-(1-tert-butoxycarbonylamino-2-methyl-propyl)-oxazol-5-yl]-7-bromo-2-oxo-2,3-dihydro-1H-indol-3-yl}-4-hydroxy-phenyl)-propionic acid methyl ester 
• 496789-54-9 2-benzyloxycarbonylamino-3-(3-{3-[4-benzyloxymethyl-2-(1-tert-butoxycarbonylamino-2-methyl-propyl)-oxazol-5-yl]-7-bromo-1-methoxymethyl-2-oxo-2,3-dihydro-1H-indol-3-yl}-4-methoxymethoxy-phenyl)-propionic acid 
• 956413-57-3 C₃₇H₃₉BrN₄O₉ 
• 100-39-0 benzyl bromide 
• 793727-79-4 {1-[4-benzyloxymethyl-5-(7-bromo-3-hydroxy-1-methoxymethyl-2-oxo-2,3-dihydro-1H-indol-3-yl)-oxazol-2-yl]-2-methyl-propyl}-carbamic acid tert-butyl ester 
• 496789-39-0 (S)-2-(1-tert-butoxycarbonylamino-2-methyl)propyloxazole-4-methanol benzyl ether 
• 496789-53-8 (S)-2-(1-tert-butoxycarbonylamino-2-methyl)propyloxazole-4-methanol 
• 158068-94-1 (S)-2-((S)-1-((tert-butoxycarbonyl)amino)-2-methylpropyl)-4,5-dihydrooxazole-4-carboxylic acid methyl ester 
• 71017-98-6 methyl (2S)-2-[(2S)-2-{[(tert-butoxy)carbonyl]amino}-3-methylbutanamido]-3-hydroxypropanoate 
• 158068-97-4 2-<(S)-1--2-methylpropyl>-4-carbomethoxyoxazole 
• 13734-41-3 t-Boc-L-valine 

Downstream Products

• 793728-21-9 C₃₈H₃₇BrN₄O₉ 
• 496789-56-1 C₃₈H₃₉BrN₄O₉ 
• 496789-57-2 C₃₈H₃₇BrN₄O₁₀ 
• 496789-58-3 C₄₈H₄₃BrN₆O₉ 
• 496789-50-5 C₄₈H₄₂N₆O₉ 
• 496789-49-2 C₄₈H₄₅BrN₆O₁₀ 

Relevant academic research and scientific papers

An expedient formal total synthesis of (-)-diazonamide A via a powerful, stereoselective O-aryl to C-aryl migration to form the C10 quaternary center

During the course of studies on the synthesis of diazonamide A 1, an unusual O-aryl into C-aryl rearrangement was discovered that allows partial control of the absolute stereochemistry of the C-10 quaternary stereogenic center. Treatment of 30 with TBAF/THF gave the O-tyrosine ethers 31 and 32 (1:1), which on heating each separately in chloroform at reflux rearranged to 33 and 34 in ratios of 84:16 and 56:44, respectively. This corresponds to a 70% yield of the correct C-10 stereoisomer 33 and a 30% yield of the wrong C-10 stereoisomer 34. Attempts to convert 34 into 33 by ipso-protonation and equilibration were unsuccessful. Confirmation of the stereochemical outcome of the rearrangement was obtained by converting 33 into 37, an advanced intermediate in the first synthesis of diazonamide A by Nicolaou et al. It was also found that the success of the above rearrangement is sensitive to the protecting group on both the tryptophan nitrogen atom and the tyrosine nitrogen atom.

Chemistry and biology of diazonamide A: First total synthesis and confirmation of the true structure

With the addition of a tenth ring, the exchange of an oxygen atom for a nitrogen in the heart of the molecule, and a different terminal residue, the revised architecture for diazonamide A (1) provided an even more challenging molecular puzzle for chemical synthesis than its predecessor. In this article, we detail the first successful total synthesis of diazonamide A, an endeavor which not only verified its proper connectivities and established the stereochemistry of its previously unassignable C-37 chiral center, but which also was attended by the development of several new synthetic strategies and tactics.