Schaefer W H, Harris T M, Guengerich F P
Arch Biochem Biophys. 1987 Aug 15;257(1):186-93. doi: 10.1016/0003-9861(87)90557-1.
Many alpha,beta-unsaturated compounds are sufficiently reactive to condense with nucleophiles under physiological conditions and are potentially deleterious to cellular processes. These compounds react with thiols by nucleophilic attack to give 1,4 addition products. We have examined the products formed from the reaction of the model thiols HSCH2CH2OH and glutathione with methylvinylmaleimide, a Michael acceptor with extended conjugation. Glutathione produced exclusively a 1,6 addition product with methylvinylmaleimide. HSCH2CH2OH also formed a 1,6 nucleophilic addition product, as well as a disubstituted product resulting from apparent further 1,4 addition to the 1,6 addition product. Two other novel products which resulted from addition to the maleimide ring and addition at the vinyl carbon proximal to the maleimide ring were observed.
许多α,β-不饱和化合物具有足够的反应活性，能够在生理条件下与亲核试剂缩合，并且可能对细胞过程有害。这些化合物通过亲核攻击与硫醇反应生成1,4-加成产物。我们研究了模型硫醇HSCH2CH2OH和谷胱甘肽与甲基乙烯基马来酰亚胺（一种具有扩展共轭的迈克尔受体）反应生成的产物。谷胱甘肽与甲基乙烯基马来酰亚胺仅生成一种1,6-加成产物。HSCH2CH2OH也形成了一种1,6-亲核加成产物，以及一种由对1,6-加成产物明显进一步进行1,4-加成而产生的二取代产物。还观察到另外两种由加成到马来酰亚胺环以及在靠近马来酰亚胺环的乙烯基碳上加成而产生的新型产物。
