Head-to-head versus head-to-tail dimerizations of transient silenes - the synthesis and reactivity of 2-(8-dimethylamino-1-naphthyl)- and 2-(4-dimethylamino-1-naphthyl)-1,1-bis(trimethylsilyl)silene

被引:6
|
作者
Hoffmann, D [1 ]
Reinke, H [1 ]
Oehme, H [1 ]
机构
[1] Univ Rostock, Fachbereich Chem, D-18051 Rostock, Germany
关键词
silenes; silaethenes; 1,3-disilacyclobutanes; 2,3-disilaphenanthren-9-on, hexahydro; Peterson reaction;
D O I
10.1016/S0022-328X(99)00218-1
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
In the absence of scavenger reagents, the transient 2-(8-dimethylamino-1-naphthyl)-1,1-bis(trimethylsilyl)silene (4), generated by a base-initiated elimination of trimethylsilanol from (8-dimethylamino-1-naphthyl)-tris(trimetylsilyl)silylmethanol (3), undergoes a spontaneous formal [2 + 2] head-to-tail cyclodimerization to give a substituted 1,3-disilacyclobutane 5, In contrast, the similarly produced 2-(4-dimethylamino-1-naphthyl)-1,1-bis(trimethysily)silene (10) dimerizes in a head-to-head mode, finally affording the hexahydro-2,3-disilaphenanthren-9-on (12). The ketone 12 is the result of a formal [2 + 4] cycloaddition of the silene 10 producing an intermediate with an enamine unit (11), which is hydrolysed during the aqueous workup to give 12. A model, explaining the different dimerization regiospecificity of the two isomeric silenes is proposed. In the presence of BH3 THF the generated silene 4 is trapped to afford 3-[bis(trimethylsilyl)silyl]-1,1-dimethyl-1-aza-2-bora-2,3-dihydrophenalene (6). All the compounds isolated, were fully characterised by IR, NMR and MS data. The compounds Z-5, 8 and E-12 were also examined by X-ray crystal structure analyses. (C) 1999 Elsevier Science S.A. All rights reserved.
引用
收藏
页码:189 / 197
页数:9
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