915315-32-1Relevant articles and documents
Total Synthesis of (?)-Salinosporamide A via a Late Stage C?H Insertion
Gholami, Hadi,Kulshrestha, Aman,Favor, Olivia K.,Staples, Richard J.,Borhan, Babak
, p. 10110 - 10113 (2019/04/25)
The synthesis of (?)-salinosporamide A, a proteasome inhibitor, is described. The synthesis highlights the assembly of a densely decorated pyrrolidinone core via an aza-Payne/hydroamination sequence. Central to the success of the synthesis is a late-stage C?H insertion reaction to functionalize a sterically encumbered secondary carbon. The latter functionalization leads to an enabling transformation where most of the prototypical strategies failed.
Total synthesis of (-)-salinosporamide A
Kaiya, Yuji,Hasegawa, Jun-Ichi,Momose, Takayuki,Sato, Takaaki,Chida, Noritaka
, p. 209 - 219 (2011/10/03)
A detailed description of our second-generation total synthesis of salinosporamideA is presented. Three contiguous stereocenters in the γ-lactam structure seen in the natural product were established by stereoselective functionalization of a D-arabinose scaffold, including an Overman rearrangement to generate a highly congested tetrasubstituted carbon center. One of the definitive reactions in the synthesis was a Lewis acid mediated skeletal rearrangement of a pyranose structure, which enabled the practical conversion of the carbohydrate scaffold to the γ-lactam structure embedded in salinosporamideA. The use of a benzyl ester as a protective group for a sterically hindered carboxylic acid led to a one-pot global deprotection at the end of the synthesis. Rearrange your chemistry! The total synthesis of anticancer natural product salinosporamideA has been achieved through a unique skeletal rearrangement (see scheme). This reaction enabled the construction of the densely functionalized γ-lactam structure found in salinosporamideA through practical methodologies including an Overman rearrangement on a D-arabinose scaffold. Copyright
Total synthesis of salinosporamide A
Endo, Atsushi,Danishefsky, Samuel J.
, p. 8298 - 8299 (2007/10/03)
Total synthesis of potent proteasome inhibitor salinosporamide A (1) has been accomplished, which features strictly substrate-controlled operations starting with the only chiral center of (R)-pyroglutamic acid. The consecutive quaternary carbons within 1 have been efficiently constructed by manipulation of two intramolecular reactions: (1) carbonate-mediated internal acylation of imidate ester (4 → 14) and (2) selenocyclization of aldehyde to exocyclic methylene group (5 → 18). Copyright
