51103-58-3Relevant articles and documents
Enantioselective total synthesis of novel diterpenoid pyrones (+)-sesquicillin and (-)-nalanthalide from fungal fermentations
Oguchi, Takamasa,Watanabe, Kazuhiro,Abe, Hideki,Katoh, Tadashi
, p. 229 - 250 (2010)
We efficiently synthesized (+)-sesquicillin (a glucocorticoid antagonist) and (-)-nalanthalide (a potassium channel Kv1.3 blocker) in a convergent and unified manner starting from (+)-5-methyl-Wieland-Miescher ketone. The synthesis involved the following key steps: (i) a [2,3]-Wittig rearrangement of a stannylmethyl ether to install the stereogenic center at C9 and the exo-methylene functionality at C8 present in the tran/decalin portion, (ii) a coupling reaction of a trans-decalin portion with a γ-pyrone moiety to assemble the requisite whole carbon framework, and (iii) a conversion of a γ-pyrone moiety to an α-pyrone ring to produce (+)-sesquicillin. The present total synthesis has verified the absolute configuration of these natural products.
An efficient stereoselective total synthesis of DL-sesquicillin, a glucocorticoid antagonist
Zhang, Fei,Danishefsky, Samuel J.
, p. 1434 - 1437 (2007/10/03)
The key step in the total synthesis of sesquicillin (3) is a stereoselective Claisen rearrangement of 1 to afford 2. The synthesis also features an efficient sequence to install an α-pyrone moiety in a hindered environment; TBS = tert-butyldimethylsilyl.