Development of New Versatile Reagents for Mitsunobu Reaction. -Utilization of Wittig Reagent as a New Mitsunobu Reagent-

Mitsunobu反应是利用偶氮二甲酸二乙酯和三苯基膦之间的氧化还原体系进行的一种常用的烷基化反应，但它只适用于pK_a小于11的亲核试剂。为了克服这一局限性，我们引入了几种偶氮二甲酰胺(TIPA、ADDP、TMAD和DHTD)与三丁基膦的组合。在我们不断寻找新的多功能试剂的过程中，我们发现氰亚甲基三烷基膦(CMBP，CMMP)能够催化各种pK_a大于11的HA的烷基化反应。利用这些试剂，N-，C-和O-亲核试剂，如对甲苯磺酰胺、活性亚甲基化合物、醇和羧酸，实现了高效的烷基化反应。将该反应应用于生物活性化合物的合成。

The Mitsunobu reaction, a popular alkylation reaction utilizing the redox system between diethyl azodicarboxylate and triphenylphosphine, has a shortcoming that it can only be applied satisfactorily to a nucleophile (HA) of PK_a less than 11, In order to overcome the limitation, we introduced several combinations of azodicarboxamides (TIPA, ADDP, TMAD, and DHTD) and tributylphosphine. In our continual search for new versatile reagents, we found cyanomethylenetrialkylphosphorane (CMBP, CMMP) was capable of mediating the alkylation of various HA of larger PK_a than 11. Utilizing these reagents, the efficient alkylation of N-, C-, and O-nucleophiles, such as tosylamides, active methylene compounds, alcohols, and carboxylic acid was accomplished. The reaction was applied for the synthesis of biologically active compounds.