School of Chemistry and Biochemistry, Georgia Institute of Technology , Atlanta, Georgia 30332-0400, United States.
Org Lett. 2017 Jun 2;19(11):2833-2836. doi: 10.1021/acs.orglett.7b00990. Epub 2017 May 16.
Furfuryl carbamates are labile and require care to be accessed by activating furfuryl alcohols. An alternative oxanorbornadiene (OND)-based strategy is presented for the preparation of 5-R-substituted furfuryl carbamates via the reactions of amines with intermediate OND carbonates. The resulting OND carbamates, which are stable for several months, undergo thiol mediated retro-Diels-Alder reaction to deliver the desired furfuryl carbamates in a single flask. Conditions for the selective hydrolysis of furfuryl carbamates in the presence of tert-butyloxycarbonyl (Boc) groups were identified, and it was shown that furfuryl carbamates can be used as a prodrug handle.
糠基氨基甲酸酯不稳定，需要小心处理才能使糠基醇活化。本文提出了一种替代的降冰片二烯（OND）基策略，通过胺与中间的 OND 碳酸酯反应来制备 5-R-取代的糠基氨基甲酸酯。得到的 OND 氨基甲酸酯在几个月内稳定，通过硫醇介导的反-Diels-Alder 反应，在一个烧瓶中一步得到所需的糠基氨基甲酸酯。本文还确定了在叔丁氧羰基（Boc）基团存在下选择性水解糠基氨基甲酸酯的条件，并表明糠基氨基甲酸酯可用作前药。
