联萘双金属化合物对胺基氯硼烷类的单转烃化反应及2-联萘基硼化合物的合成  

Single Site Transarylation of 2,2'- Dimetallized 1,1 Binaphthyl to Aminochloroboranes, Synthesis of 2 - Binaphthyl boron compounds

作　　者：袁国正[1] 桂国球[1] 

机构地区：[1]武汉大学化学系,湖北武汉430072

出　　处：《有机化学》1996年第2期139-144,共6页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金

摘　　要：一类新反应现象被描述。2.2′-二锂联萘或2.2′-双格氏化联萘当与Et_2NBCl_2及Et_2NB(Ph)Cl反应时,仅以一个M—C键参与亲核烃化,另一M—C键因可能的七员环过渡态而失活。反应分别给出仅在联萘2-位取代的硼化合物Ⅲ或Ⅳ,而得不到2,2′-双位取代的硼化合物Ⅰ或Ⅲ。五个新硼化合物被合成,并讨论了反应机理。Reaction of 2,2'- dilithio (or dibromomagnesio) - 1,1'- binaphthyl with 2 eqiv. of (N, N - diethylamino) phenylchloroborane, or quimolar amounts of diethylaminodichloroborane, followed by hydrolysis and chelati on with N, O - bidentate ligands, afforded the unexpected (2 -binaphthyl)phenylboron chelates Ⅱ or bis( 2 - binaphthyl) boron chelates Ⅳ respectively, instead of the expected 1,1'- binaphtyl - 2,2'- bis (phenylboryi) chelates Ⅰ or dinaphthbborole derivatives Ⅲ. These evidences show that the only one M- C bond in 2,2'-dimetallized 1,1'-binaphthyl participates in the nucleophilic reaction with aminochloroboranes and another M - C bond loses its transarylation activity. The reaction mechanism in connection with a possible 7 - membered ring transition state was describedion.

关 键 词：胺基硼烷 联萘 二烃基硼化合物 烃化反应 

分 类 号：O627.31[理学—有机化学]