Nandi Rhituparna, Niyogi Sovan, Kundu Sourav, Gavit Vipin R, Munda Mintu, Murmu Ranjit, Bisai Alakesh
Department of Chemistry, Indian Institute of Science Education and Research Bhopal Bhopal Bypass Road Bhopal 462 066 Madhya Pradesh India
Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur Campus Kalyani, Nadia 741 246 West Bengal India.
Chem Sci. 2023 Jun 20;14(30):8047-8053. doi: 10.1039/d2sc07119c. eCollection 2023 Aug 2.
N-N dimeric indolosesquiterpene alkaloids constitute a class of under-investigated architecturally intriguing natural products. Herein, we report the first chemical oxidation approach to the asymmetric total syntheses of these atropisomeric indolosesquiterpenoids through N-N bond formation. Specifically, dixiamycins A (1a) and B (1b) were prepared through a Cu(i)-mediated aerobic dehydrogenative dimerization from the naturally occurring monomer xiamycin A methyl ester (2b); this preparation also represents the first total synthesis of dixiamycin A (1a). The monomer xiamycin A methyl ester (2b) was synthesized a late-stage Buchwald Pd(ii)-mediated aerobic dehydrogenative C-N bond formation.
N-N二聚吲哚倍半萜生物碱是一类研究较少但结构引人入胜的天然产物。在此，我们报道了通过形成N-N键对这些阻转异构吲哚倍半萜进行不对称全合成的首次化学氧化方法。具体而言，通过铜（I）介导的需氧脱氢二聚反应，由天然存在的单体夏霉素A甲酯（2b）制备了双夏霉素A（1a）和B（1b）；该制备方法也代表了双夏霉素A（1a）的首次全合成。单体夏霉素A甲酯（2b）是通过后期布赫瓦尔德钯（II）介导的需氧脱氢C-N键形成反应合成的。
