214914-80-4

Upstream product

• 214914-87-1 (R)-tert-butyl((1-((4-methoxybenzyl)oxy)pent-4-yn-2-yl)oxy)dimethylsilane 
• 214914-86-0 1-(4-Methoxybenzyloxy)pent-4-yn-2-ol 
• 80910-01-6 (R)-2-(((4-methoxybenzyl)oxy)methyl)oxirane 
• 214914-88-2 (R)-5-(tert-Butyl-dimethyl-silanyloxy)-6-(4-methoxy-benzyloxy)-hex-2-ynoic acid methyl ester 
• 922-67-8 propynoic acid methyl ester 

Downstream Products

• 807363-99-1 methyl (2Z,5R)-5-hydroxy-6-(4-methoxybenzyloxy)-3-prop-2-enylhex-2-enoate 
• 214914-83-7 (R)-6-(4-Methoxy-benzyloxy)-5-(1-methoxycarbonyl-vinyloxy)-hex-2-ynoic acid methyl ester 
• 214914-82-6 2-Dimethylaminomethyl-2-[(R)-1-(4-methoxy-benzyloxymethyl)-4-methoxycarbonyl-but-3-ynyloxy]-malonic acid dimethyl ester 
• 807364-57-4 (4S,7E,12R)-4-benzyloxy-12-tert-butyldimethylsilyloxy-10-[(Z)-2-tert-butyldimethylsilyloxyethylidene]-13-(4-methoxybenzyloxy)-5,5-dimethyltrideca-1,7-dien-6-one 
• 807365-45-3 (6R,2RS)-4-[(Z)-2-tert-butyldiphenylsilyloxyethylidene]-6-trimethylsilyloxy-7-(4-methoxybenzyloxy)heptane-1,2-diol 
• 807365-39-5 (2R)-4-[(Z)-2-tert-butyldiphenylsilyloxyethylidene]-2-trimethylsilyloxy-1-(4-methoxybenzyloxy)hept-6-ene 
• 807365-52-2 (5R)-3-[(E)-2-tert-butyldiphenylsilyloxyethylidene]-6-(4-methoxybenzyloxy)-5-trimethylsilyloxyhexanal 
• 807366-26-3 (2R)-4-[(Z)-2-tert-butyldiphenylsilyloxyethylidene]-1-(4-methoxybenzyloxy)hept-6-en-2-ol 
• 807364-05-2 (Z,6R)-6-tert-butyldimethylsilyloxy-4-(2-tert-butyldimethylsilyloxyethylidene)-7-(4-methoxybenzyloxy)hept-1-ene 
• 807364-12-1 (E,5R)-5-tert-butyldimethylsilyloxy-3-(2-tert-butyldimethylsilyloxyethylidene)-6-(4-methoxybenzyloxy)hexanal 
• 807365-33-9 (Z,6R)-4-(2-hydroxyethylidene)-7-(4-methoxybenzyloxy)hept-1-en-6-ol 
• 214914-81-5 2-[(R)-1-(4-Methoxy-benzyloxymethyl)-4-methoxycarbonyl-but-3-ynyloxy]-malonic acid dimethyl ester 

Relevant academic research and scientific papers

The evolution of a stereoselective synthesis of the C1-C16 fragment of bryostatins

The development of a synthesis of the C1-C16 fragment of bryostatins in which the key step is a stereoselective oxy-Michael reaction used to assemble the cis-2,6-disubstituted tetrahydropyran with the exocyclic alkene already installed, is described. Foll

A stereoselective synthesis of the C(1)-C(16) fragment of the bryostatins

A synthesis of the C(1)-C(16) fragment of the brysostatins has been developed. Key steps are the stereoselective copper(I) catalysed addition of allylmagnesium bromide to an alkynyl ester, a condensation of a βγ-unsaturated aldehyde with a ketophosphonate

An approach to the C(10)-C(16) fragment of the bryostatins: Stereoselective exocyclic double-bond formation by vinyl radical cyclization

On treatment with tributyltin hydride, the vinyl bromide 11 and the vinyl iodide 26 cyclize to give mixtures of the (E)- and (Z)-4-(alkoxycarbonylmethylene)tetrahydropyrans 12/13 and 27/28 in which the (E)-isomers 12 and 27 are the major components accounting for 80% of the products. Addition of triphenyltin hydride to the alkyne 34 similarly initiates cyclization giving a mixture of products 35-37, the composition of the mixture depending upon the concentration of the tin hydride. These results are consistent with faster cyclization of the (Z)-vinyl radical with kinetic formation of five-membered ring containing products which are either trapped by hydrogen transfer from the tin hydride or which rearrange to form a 4-methylenetetrahydropyran. This chemistry was applied to prepare the cis-2,6-disubstituted 4-(methoxycarbonylmethylene)tetrahydropyran 50 which may be useful for the introduction of the C(10)-C(16) fragment into the bryostatins. Cyclization of the p-methoxybenzyl protected vinyl iodide 58 is less stereoselective, perhaps because of intramolecular hydrogen transfer from the p-methoxybenzyl group.