220634-80-0

Upstream product

• 91751-24-5 (R)-3-[(tert-butyldiphenylsilyl)oxy]-2-methylpropanal 
• 121887-95-4 (R)-(+)-3-butyn-2-ol methanesulfonate 
• 95514-03-7 (R)-methyl 3-(tert-butyl(diphenyl)silyloxy)-2-methylpropanoate 
• 58479-61-1 tert-butylchlorodiphenylsilane 

Downstream Products

• 263138-29-0 (2R,3S,4S)-(tert-butyldiphenylsilyl)oxy-2,4-dimethyl-3-(methoxymethoxy)-5-hexyne 
• 263138-32-5 (2R,3S,4S,7S,8R,9R,10R)-3,9-bis(methoxymethoxy)-1-(tert-butyldiphenylsilyl)oxy-12-(4-methoxybenzyloxy)-7-(4-nitrobenzoyl)-2,4,8,10-tetramethyl-5-hexyne 
• 263138-34-7 tert-Butyl-[(2R,3S,4S,7R,8S,9R,10R)-12-(4-methoxy-benzyloxy)-3,7,9-tris-methoxymethoxy-2,4,8,10-tetramethyl-dodecyloxy]-diphenyl-silane 
• 263138-33-6 (3R,4R,5S,6R,9S,10S,11R)-12-(tert-Butyl-diphenyl-silanyloxy)-1-(4-methoxy-benzyloxy)-4,10-bis-methoxymethoxy-3,5,9,11-tetramethyl-dodecan-6-ol 
• 263138-31-4 (2R,3S,4S,7S,8R,9R,10R)-3,9-bis(methoxymethoxy)-1-(tert-butyldiphenylsilyl)oxy-12-(4-methoxybenzyloxy)-2,4,8,10-tetramethyl-5-dodecyn-7-ol 
• 263138-30-3 (2R,3S,4S,7R,8R,9R,10R)-3,9-bis(methoxymethoxy)-1-(tert-butyldiphenylsilyl)oxy-12-(4-methoxybenzyloxy)-2,3,8,10-tetramethyl-5-dodecyn-7-ol 
• 263138-37-0 (E)-(4R,5S,6S,9R,10S,11R,12R)-14-(4-Methoxy-benzyloxy)-5,9,11-tris-methoxymethoxy-4,6,10,12-tetramethyl-tetradec-2-enoic acid ethyl ester 
• 263138-39-2 {(2R,3R)-3-[(1S,2S,3S,6R,7S,8R,9R)-11-(4-Methoxy-benzyloxy)-2,6,8-tris-methoxymethoxy-1,3,7,9-tetramethyl-undecyl]-oxiranyl}-methanol 
• 263138-40-5 (2S,3R)-2-Iodomethyl-3-[(1S,2S,3S,6R,7S,8R,9R)-11-(4-methoxy-benzyloxy)-2,6,8-tris-methoxymethoxy-1,3,7,9-tetramethyl-undecyl]-oxirane 
• 263138-38-1 (E)-(4R,5S,6S,9R,10S,11R,12R)-14-(4-Methoxy-benzyloxy)-5,9,11-tris-methoxymethoxy-4,6,10,12-tetramethyl-tetradec-2-en-1-ol 
• 263138-41-6 (3S,4R,5S,6S,9R,10S,11R,12R)-14-(4-Methoxy-benzyloxy)-5,9,11-tris-methoxymethoxy-4,6,10,12-tetramethyl-tetradec-1-en-3-ol 
• 263138-35-8 (2R,3S,4S,7R,8S,9R,10R)-12-(4-Methoxy-benzyloxy)-3,7,9-tris-methoxymethoxy-2,4,8,10-tetramethyl-dodecan-1-ol 
• 263138-36-9 (2S,3S,4S,7R,8S,9R,10R)-12-(4-Methoxy-benzyloxy)-3,7,9-tris-methoxymethoxy-2,4,8,10-tetramethyl-dodecanal 

Relevant academic research and scientific papers

Stereoselective synthesis of C5-C20 and C21-C34 subunits of the core structure of the aplyronines. Applications of enantioselective additions of chiral allenylindium reagents to chiral aldehydes

The stereoselective synthesis of a C5-C20 and a C21-C34 subunit of the aplyronine family of polyketide marine macrolides has been achieved. These subunits contain all 15 stereocenters of the core structure. Six of the 15 stereocenters were introduced through enantioselective and diastereoselective additions of chiral allenylindium reagents to α-methyl-β-oxygenated propionaldehydes. The products of these additions were further transformed by reactions involving the terminal alkynyl substituent produced in the addition reactions. Unlike previous applications of this methodology, the present synthesis employs Pd(0)-catalyzed transmetalations of chiral allenylpalladium intermediates to generate the chiral allenylindium reagents in situ.

Preparation of Chiral Allenylmetal Reagents from Enantioenriched Allenyl Iodides and Propargylic Mesylates. A Comparison of Indium, Bismuth, and Tin Derivatives

Chiral allenylmetal halides were prepared starting from enantioenriched (～95% ee) 1-octyn-3-ol mesylate (1) and 3-butyn-2-ol mesylate (7). Addition of these transient metallo species to aldehydes in situ afforded mainly anti homopropargylic alcohol adduct

Addition of allenylzinc reagents, prepared in situ from nonracemic propargylic mesylates, to aldehydes. A new synthesis of highly enantioenriched homopropargylic alcohols

Enantioenriched propargylic mesylates are converted to chiral allenylzinc reagents via transient allenylpalladium species by treatment with a Pd(0)-phosphine catalyst in the presence of excess Et2Zn. These zinc reagents undergo S(E)2' additions to various aldehydes to yield mainly the anti homopropargylic alcohol adducts of high ee. The reaction is most efficient in THF with Pd(OAc)2· PPh3 as the catalyst precursor. As little as 2.5 mol % of this precursor is effective.