Li Zaiguo, Baker Daniel L, Tigyi Gabor, Bittman Robert
Department of Chemistry and Biochemistry, Queens College of the City University of New York, Flushing, New York 11367-1597, USA.
J Org Chem. 2006 Jan 20;71(2):629-35. doi: 10.1021/jo052030w.
[reaction: see text] Lysophosphatidic acids bearing a benzophenone group in either the sn-1 or sn-2 chain of an oleoyl-type ester or oleyl-type ether chain and (32)P in the phosphate group were synthesized. The benzophenone moiety was introduced by selective hydroboration of the double bond of enyne 11 at low temperature, followed by a Suzuki reaction with 4-bromobenzophenone. The key intermediates for the preparation of ester-linked lysophosphatidic acid (LPA) 1 and 3 were obtained in one pot by a modified DIBAL-H reduction of orthoformate intermediate 22. These probes were shown to covalently modify a single protein target in rat plasma containing albumin and several protein targets in rat plasma containing a low level of albumin.
[反应：见正文] 合成了在油酰基型酯或油烯基型醚链的sn-1或sn-2链中带有二苯甲酮基团且磷酸基团中含有(32)P的溶血磷脂酸。二苯甲酮部分是通过在低温下对烯炔11的双键进行选择性硼氢化，然后与4-溴二苯甲酮进行铃木反应引入的。通过对原甲酸酯中间体22进行改进的二异丁基氢化铝（DIBAL-H）还原，一锅法得到了制备酯连接溶血磷脂酸（LPA）1和3的关键中间体。这些探针被证明能共价修饰含有白蛋白的大鼠血浆中的单一蛋白质靶点以及含有低水平白蛋白的大鼠血浆中的多个蛋白质靶点。
