Department of Chemistry, Jadavpur University, Jadavpur, Kolkata, 700032, West Bengal, India.
Department of Chemistry, Jadavpur University, Jadavpur, Kolkata, 700032, West Bengal, India.
Carbohydr Res. 2021 Dec;510:108452. doi: 10.1016/j.carres.2021.108452. Epub 2021 Sep 27.
A straightforward synthesis of (+)-trans-(4S,5R)- and (+)-cis-(4R,5R)-whisky lactones starting from d-(+)-mannitol has been reported here in fewer number of efficient steps compared to existing literature processes involving d-mannitol as the chiral pool starting material. Chiron approach directly translated chirality of d-mannitol to one of the two chiral centers in these target molecules. Toward this end, stereoisomerically pure trans- and cis-iodomethyl-γ-lactones were formed in the penultimate step. These two acted as versatile advanced common intermediates as they were also converted to the (+)-trans-(4S,5R)- and (+)-cis-(4R,5R)-cognac lactones, respectively. To the best of our knowledge, till date no synthesis of cognac lactones starting from d-mannitol has been reported. All these lactones are identified as the key aroma components of aged alcoholic beverages.
与现有文献中以 d-甘露醇为手性源的工艺相比，本文报道了一种更为简洁高效的方法，从 d-(+)-甘露醇出发，直接合成了 (+)-反式-(4S,5R)-和 (+)-顺式-(4R,5R)-威士忌内脂。前手性 approach 直接将 d-甘露醇的手性转化为这两个目标分子中两个手性中心之一。为此，在倒数第二步中形成了立体异构体纯的反式和顺式碘甲基-γ-内脂。这两种物质都可以作为多功能的高级通用中间体，因为它们也分别转化为 (+)-反式-(4S,5R)-和 (+)-顺式-(4R,5R)-干邑内脂。据我们所知，迄今为止，还没有从 d-甘露醇开始合成干邑内脂的报道。所有这些内脂都是陈年老酒的关键香气成分。
