Institute of Organic Chemistry, University of Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
Molecules. 2011 Jun 7;16(6):4695-718. doi: 10.3390/molecules16064695.
Starting from 2-(triphenylsilyl)ethanol a new oxycarbonyl protecting group cleavable by fluoride ion induced Peterson-elimination has been developed. Known 2-(triphenylsilyl)ethanol has been prepared from commercially available triphenylvinyl-silane by a hydroboration-oxidation sequence using the sterically hindered borane reagent 9-BBN. The silyl alcohol was subsequently transformed into its chloroformate, imidazolylcarboxylic acid ester and p-nitrophenyl carbonate and used in standard protocols for the formation of carbamates and carbonates. The Tpseoc group proved to be highly resistant against acidic conditions applied in removal of tert-butyl esters and the t-Boc-group. It also withstood catalytic hydrogenation, treatment with morpholine, methylhydrazine and Pd-reagents/allyl-scavanger combinations, conditions required to cleave Cbz-, Fmoc-, phthalimide- and Alloc-groups. The Tpseoc-group is cleaved upon treatment with TBAF/CsF at 0 °C or r.t. with cleavage times reaching from.
从 2-（三苯甲硅基）乙醇出发，开发了一种可通过氟离子诱导的 Peterson 消除反应裂解的新的氧羰基保护基。已知的 2-（三苯甲硅基）乙醇是通过使用空间位阻硼烷试剂 9-BBN 对商业可得的三苯乙烯基硅烷进行硼氢化-氧化序列制备的。硅醇随后被转化为其氯甲酸酯、咪唑羧酸酯和对硝基苯碳酸盐，并用于形成氨基甲酸酯和碳酸酯的标准方案中。Tpseoc 基团被证明对用于去除叔丁酯和 t-Boc 基团的酸性条件具有高度抗性。它还能耐受催化氢化、吗啉处理、甲基肼和 Pd-试剂/烯丙基清除剂组合的条件，这些条件是裂解 Cbz-、Fmoc-、邻苯二甲酰亚胺-和Alloc-基团所必需的。Tpseoc 基团在 0°C 或室温下用 TBAF/CsF 处理时会裂解，裂解时间从.
