Development and application of allyl, 2-sulfonylethyl and 2-thioethyl carbamate linkers for solid phase N-acyliminium ion chemistry.

J. Maarseveen, Wim J. N. Meester, J. Veerman, C. G. Kruse, P. Hermkens, F. Rutjes, H. Hiemstra
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引用次数: 4

Abstract

We have evaluated the allyl, 2-sulfonylethyl (SEC) and 2-thioethyl (TEC) carbamate linker systems for their application in solid supported N-acyliminium ion chemistry. As model reactions the syntheses of both homoallylic amines (via a three component protocol starting from an immobilised primary carbamate) and 2-substituted pyrrolidines (via carbamate bound 4,4-diethoxy-2-phenylbutylamine) were conducted. The required precursor p-nitrophenyl carbonate resins were prepared in high yields from cheap starting materials. All linkers proved to be stable under the required cationic reaction conditions. A serious drawback of the allyl carbamate linker is the tedious work up procedure which is required for the removal of the remains of the cleavage cocktail. The SEC linker is excellently stable to both Lewis and protic acidic conditions combined with a moderate base stability thus allowing the use of amines as reactants or bases in subsequent reactions. Cleavage of SEC linker bound amines was easily effected by treatment of the resins with a cocktail of 1 M NaOMe in THF–MeOH (2 ∶ 1). The widest synthetic scope was found with the TEC linker which combined a sufficient stability against the cationic conditions required for N-acyliminium ion chemistry with complete stability under basic conditions. Cleavage of TEC linker bound amines could be effected by treatment with strong acid or by oxidation of the sulfide to the sulfone (to give the SEC linker) followed by addition of the basic cleavage cocktail.
烯丙基、2-磺基乙基和2-硫乙基氨基甲酸酯固相n -酰基离子化学连接剂的开发与应用。
我们评价了烯丙基、2-磺基乙基(SEC)和2-硫乙基(TEC)氨基甲酸酯连接体系在固载n -酰基离子化学中的应用。作为模型反应,均烯丙基胺(通过从固定氨基甲酸酯开始的三组分方案)和2-取代吡咯烷(通过氨基甲酸酯结合4,4-二氧基-2-苯基丁胺)的合成进行。以低廉的原料制备了所需的前驱体对硝基苯基碳酸酯树脂。在要求的阳离子反应条件下,所有的连接剂都是稳定的。氨基甲酸烯丙酯连接剂的一个严重缺点是繁琐的工作程序,需要去除裂解鸡尾酒的残留物。SEC连接剂在路易斯酸和质子酸条件下都非常稳定,并且具有中等的碱稳定性,因此可以在随后的反应中使用胺作为反应物或碱。用1 M NaOMe在THF-MeOH(2∶1)中混合处理后,可使SEC连接剂结合的胺类化合物裂解。TEC连接剂的合成范围最广,它在n -乙酰基离子化学所需的阳离子条件下具有足够的稳定性,在碱性条件下具有完全的稳定性。用强酸处理或将硫化物氧化为砜(得到SEC连接剂),然后加入碱性裂解鸡尾酒,可以影响TEC连接剂结合胺的裂解。
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