714974-22-8

Upstream product

• 18162-48-6 tert-butyldimethylsilyl chloride 
• 335060-49-6 (2S,4R)-5-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-2,4-dimethylpentyl acetate 
• 90270-02-3 (2R,4S)-1-hydroxy-2,4-dimethylpentyl acetate 
• 147782-80-7 (2S,4R)-5-(tert-butyl(dimethyl)silyloxy)-2,4-dimethyl-1-pentanol 
• 58479-61-1 tert-butylchlorodiphenylsilane 

Downstream Products

• 157837-64-4 (2R,4S)-5-{[tert-butyl(diphenyl)silyl]oxy}-2,4-dimethylpentan-1-ol 
• 714974-18-2 (1''S,1'''R,2'''R,3S,4S,6S,8R,10S)-3-(tert-butyldimethyl-silyloxy)-4,6,8,10-tetramethyl-11-(tetrahydropyran-2'-yloxy)undecanoic acid 6''-bromo-6''-cyano-1-[2'''-(4'''-methoxymenzyloxymethyl)cyclopentyl]hexa-3''E,5''E-dienyl ester 
• 714974-20-6 (1'R,2S,2'R,8R,9S,11R,13S,15S,16S)-9,16-bis(tert-butyldimethylsilyloxy)-2-[2'-(4''-methoxybenzyloxymethyl)cyclopentyl]-9,11,13,15-tetramethyl-18-oxo-oxaoctadeca-4E,6Z-diene-7-carbonitrile 
• 714974-19-3 (1'S,1''R,2''R,3S,4S,6S,8R,10S)-3-(tert-butyldimethylsilyloxy)-11-hydroxy-4,6,8,10-tetramethylundecanoic acid 6''-bromo-6''-cyano-1-[2'''-(4'''-methoxymenzyloxymethyl)cyclopentyl]hexa-3''E,5''E-dienyl ester 
• 714974-07-9 (2S,4E,6Z,8R,9S,11R,13S,15S,16S)-16-(tert-butyldimethylsilyloxy)-8-hydroxy-2-{(1R,2R)-2-[(4-methoxybenzyloxy)methyl]cyclopentyl}-9,11,13,15-tetramethyl-18-oxooxacyclooctadeca-4,6-diene-7-carbonitrile 
• 714974-06-8 (2S,4E,6Z,8S,9S,11R,13S,15S,16S)-16-(tert-butyldimethylsilyloxy)-8-hydroxy-2-{(1R,2R)-2-[(4-methoxybenzyloxy)methyl]cyclopentyl}-9,11,13,15-tetramethyl-18-oxooxacyclooctadeca-4,6-diene-7-carbonitrile 
• 714973-93-0 (1'S,1''R,2''R,3S,4S,6S,8R,10S)-3-(tert-butyldimethylsilyloxy)-4,6,8,10-tetramethyl-11-oxoundecanoic acid 6''-bromo-6''-cyano-1-[2'''-(4'''-methoxymenzyloxymethyl)cyclopentyl]hexa-3''E,5''E-dienyl ester 
• 714974-10-4 (3'S,4R,4'S,6'S,8'R,10'S)-4-benzyl-3-[3'-hydroxy-4',6',8',10'-tetramethyl-11'-(tetrahydropyran-2''-yloxy)undecanoyl]-2-oxazolidinone 
• 714974-12-6 (2S,4S,6R,8S)-1-(tert-butyldiphenylsilyloxy)-2,4,6,8-tetramethyl-9-(tetrahydropyran-2'-yloxy)nonane 
• 714974-08-0 (2S,6R,8S)-9-(tert-butyldiphenylsilyloxy)-1-(4'-methoxybenzyloxy)-2,6,8-trimethylnon-3-yne 
• 714973-97-4 (-)-(2S,4R,6S,8S)-9-(tert-butyl-diphenyl-silyloxy)-2,4,6,8-tetramethyl-nonan-1-ol 
• 714973-95-2 (2S,6R,8S)-9-(tert-butyldiphenylsilyloxy)-2,6,8-trimethylnon-3-yn-1-ol 
• 157837-65-5 (2R,4S)-5-{[tert-butyl(diphenyl)silyl]oxy}-2,4-dimethylpentanal 
• 7184-60-3 borrelidin 

Relevant academic research and scientific papers

Synthesis of the alkaloid tyroscherin by an aldol/Curtius strategy

The alkaloid tyroscherin (2), which contains a vicinal anti-amino alcohol subunit was prepared from 4-hydroxyphenylpropionic acid (5) and meso-diol 9. After desymmetrization of diol 9 and suitable protecting group manipulations, one terminus was extended via a Claisen rearrangement giving rise to enoate ent-15. The missing carbon on the other end could be incorporated using MeMgCl/CuBr·SMe2 leading eventually to aldehyde ent-22. The acylated oxazolidinone 32 derived from acid 5 and aldehyde ent-22 were combined in an aldol reaction. A subsequent Curtius rearrangement on the carboxylic group furnished the amino function of tyroscherin (2). In a proof of concept study the same strategy was used to prepare tyroscherin analog 28.

Total synthesis of borrelidin

(Chemical Equation Presented) The total synthesis of borrelidin has been achieved. The best feature of our synthetic route is macrocyclization at C11-C12 for the construction of an 18-membered ring after esterification between two segments. A detailed examination of the macrocyclization led us to the samarium(II) iodide-mediated intramolecular Reformatsky-type reaction as the most efficient synthetic approach. The two key segments were synthesized through regioselective methylation, directed hydrogenation, stereoselective Reformatsky-type reaction, and MgBr2·Et2O-mediated chelation-controlled allylation.

Total synthesis of (-)-borrelidin

Matrix presented. The total synthesis of borrelidin has been achieved. The best feature of our synthetic route is Sml2-mediated intramolecular Reformatsky-type reaction for macrocyclization after esterification between two segments. The two key segments were synthesized through chelation-controlled carbotitanation, chelation-controlled hydrogenation, stereoselective Reformatsky reaction, and MgBr2·Et2O-mediated chelation-controlled allylation.