118977-92-7Relevant articles and documents
Efficient Degradation of FK-506 to a Versatile Synthetic Intermediate
Askin, D.,Joe, Daisy,Reamer, R. A.,Volante, R. P.,Shinkai, I.
, p. 5451 - 5454 (2007/10/02)
An 11-step degradation of natural FK-506 (1) to selectively protected C10-C34 synthetic intermediate 2 has been accomplished in 14percent overall yield.The key steps include; (a) lead tetracetate mediated C9-C10 bond cleavage of 24,32-bis(triisopropylsilyl)-FK-506 (3), (b) simultaneous C10 ester, C22 ketone reduction/C26 oxygen deacylation, and (c) selective bis(triethylsilylation) of the resulting triols 7a,b.The degradate 2 is ready for reacylation at the C26 hydroxyl terminus; hydrolysis of the dimethyl acetal moiety then provides an aldehyde ready for homologation at the C10 terminus.
A Formal Synthesis of FK-506. Exploration of Some Alternatives to Macrolactamization
Jones, A. Brian,Villalobos, Annabella,Linde, Robert G.,Danishefsky, Samuel J.
, p. 2786 - 2797 (2007/10/02)
The coupling of the previously described subunits 2, 3, and 4 is described.The C28-C27 E-double bond is fashioned from a sulfurane induced dehydration of alcohol 11.The C19-C20 E-double bond was constructed via a modified Julia process culminating in a reductive elimination of a vicinal trifluoroacetoxy sulfone (see 22 -> 23 -> 24 and 25).The synthesis of intermediates anticipating potential macrolactonization are also described.
