REACTIONS OF THE CARBANION FROM AN ORSELLINATE DERIVATIVE WITH ELECTROPHILES
REACTIONS OF THE CARBANION FROM AN ORSELLINATE DERIVATIVE WITH ELECTROPHILES
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DOI：
10.1039/p19840001043
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发表时间：
1984-01-01
期刊：
影响因子：
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通讯作者：
WILKINSON, MR
中科院分区：
文献类型：
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作者：
CARPENTER, TA;EVANS, GE;WILKINSON, MR
作为第二次亲核攻击的结果，烷基锂试剂攻击Orsellinic酸二甲基醚(11)的酯，得到酮和在某些情况下较少量的烯烃。在零下78度。其自身的阴离子(10)对11的攻击速度足够慢，以至于二异丙胺锂几乎可以定量地产生该阴离子。10与各种简单的亲电试剂(D2O、CO2、MEL、Me3SiCl和Me3SnCl)反应，得到预期的亲核加成产物。与醛(PhCHO和MECHO)一起，最初形成的酒精内酯化为二氢异香豆素。阴离子与乙酰氯发生酰化反应得到酮。三甲基硅基衍生物的反应在大多数情况下与母体化合物(11)非常相似；三甲基锡基衍生物用Meli或BunLi处理后再生10。最后，10与α-吡喃酮反应，出人意料地得到了萘吡喃酮。
Esters of orsellinic acid dimethyl ether (11) were attacked by alkyl-lithium reagents to give ketones and in some cases smaller amounts of alkenes as a result of a 2nd nucleophilic attack. At -78.degree. C attack on 11 by its own anion (10) was sufficiently slow that the anion could be generated almost quantitatively by lithium di-isopropylamide. Reactions of 10 with various simple electrophiles (D2O [deuterium], CO2, Mel, Me3SiCl and Me3SnCl) gave the expected products of nucleophilic addition. With aldehydes (PhCHO and MeCHO) the initially formed alcohol lactonized to give a dihydroisocoumarin. The anion was acylated with acetyl chloride to give a ketone. The reactions of a trimethylsilyl derivatives were in most cases very similar to the parent compound (11); the trimethylstannyl derivative regenerated 10 on treatment with MeLi or BunLi. Finally, reaction of 10 with .alpha.-pyrone unexpectedly gave a naphthopyrone.