Nandy Monosij, Das Apurba, Niyogi Sovan, Khatua Arindam, Jana Debgopal, Bisai Alakesh
Department of Chemical Sciences, IISER Kolkata, Mohanpur Campus, Kalyani, Nadia 741 246, West Bengal, India.
Department of Chemistry, IISER Bhopal, Bhopal Bypass Road, Bhauri, Bhopal 462 066, Madhya Pradesh, India.
Org Lett. 2024 Dec 13;26(49):10424-10429. doi: 10.1021/acs.orglett.4c03026. Epub 2024 Oct 10.
(+)-Brevianamides A () and B () are distinguished by their unique bicyclo[2.2.2]diazaoctane structure and have captured the interest of synthetic chemists due to their fascinating array of biological activities. The biosynthetic proposal of these classes of alkaloids led to the discovery of a number of interesting strategies. We present a biomimetic synthesis of these alkaloids starting from naturally occurring 4-hydroxy-l-proline and L-tryptophan. Gratifyingly, we emulate an alternative biosynthetic process through a unique elimination-isomerization sequence triggered by a dual-base system to generate the key -diene required for the Diels-Alder reaction to craft the bicyclo[2.2.2]diazaoctane structure.
（+）-短杆菌酰胺A（ ）和B（ ）因其独特的双环[2.2.2]二氮杂辛烷结构而与众不同，并且由于其一系列迷人的生物活性而引起了合成化学家的兴趣。这些生物碱类别的生物合成提议导致了许多有趣策略的发现。我们报道了一种从天然存在的4-羟基-L-脯氨酸和L-色氨酸出发的这些生物碱的仿生合成。令人欣慰的是，我们通过由双碱系统引发的独特消除-异构化序列模拟了另一种生物合成过程，以生成狄尔斯-阿尔德反应构建双环[2.2.2]二氮杂辛烷结构所需的关键二烯。
