2001 年第21卷有機化學(xué)\ul.21. 2001第11期,898 ~ 903Chiner Joumal of Onpnic CarmistryNo. 1.898 ~ 903●研究成果報告.輔酶NADH模型物還原活化烯烴反應(yīng)機理研究劉有成"a.b李勁“("中國科學(xué)技術(shù)大學(xué)化學(xué)系合 肥230026)06 A(*蘭州大學(xué)應(yīng)用有機化學(xué)國家重點實驗室蘭州 730000)摘要對本課題組近年來研究的輔酶NADH模型物還原活化烯烴的反應(yīng)機理進(jìn)行了綜述。劉于鋪酶模型物還原2-澳小苯其亞乙基內(nèi)二腈類化合物的反應(yīng).依賴輔酶模型物和底物的結(jié)構(gòu)，反應(yīng)可以按一步的負(fù)氫轉(zhuǎn)移機理或按電了轉(zhuǎn)移機理進(jìn)行。用手性輔酶模型物進(jìn)行這一反應(yīng).叮得到其有中等光學(xué)活性的環(huán)丙烷銜生物。實驗結(jié)果表明輔酶模型物BNAH與1.1二舉基-2.2-二硝基乙烯的反應(yīng)的過渡態(tài)具有部分雙自由基和部分共價鍵形成的特征,為Pross Shaik“曲線交叉模型"所預(yù)測的“中間機理"提供了直接的證據(jù)。BNAH與9-業(yè)芴基丙-二腈的反應(yīng)經(jīng)歷電子轉(zhuǎn)移和負(fù)電荷在9-位碳上的碳負(fù)離子中間體,動力學(xué)同位素效應(yīng)為2.6。關(guān)鍵詞輔酶 NADH還原,反應(yīng)機理,負(fù)氫轉(zhuǎn)移,單電子轉(zhuǎn)移.曲線交叉模型Study on the Mechanism of Reduction of Activated Ethyleneswith Coenzyme NADH ModelsLIU You-Cheng"aib，L Jing"(° Departmert of Chenaitry. Uniresity of Srience and Technology of China, 230026 Hegfei)(“National Laboratory of Aplied Organir Chemstry. Lanzhuu Unirerity ，730000 Imnzhou)Abstract The reduction of a series of 2-bromo- 1-(X-pheny!)ethylidene malonic derivatives with Coenzyme NADHmodels has been investigated. Depending on the structure of substrates and that of the model, hydride transfer mechanismand electron transfer mechanism could be diferentated. Thus， the reaction of 4-benzyl-I ，4-dihydronicotinamide( BNAH) with 2-brurno-l-phenyethylidenemalononitrile produced 2-penylcyclopropane-l, l-dinitrile through hydnidetransfer mechanism, while the reaction of 10-methyl-9, 1-dihydracridine with 2-bromo-1-phenylethylidenemalonontilegave I-phenyletbylidenenalontrle through electon transfer, debromination and hydrogen abstaction mechanism. Sudics on substiuent efet and kinetic isotope ef suppor the eunclusion. Using (5S)-benzy)-3-( polyul6iny)-1,4,dihydropyridine as a chiral NADH model, the synthesis of phenylcyclopropane derivatives with moderate optical activityhas been achieved. Based on the evidence of kinetic isotope ef.et and tapping with oxygen, the reduction of 1,1dipheny-2.2-dinitoethylene with BNAH has been shown to proceed through a transition state of partial diradical and par-tial covalent bonding character. This was caused by sterie hindrance of the subtuent phenyl and mitro groups as demon-strated by X-ray srstalogaphic analysis of the subtrate molecule. This provides eridence for the existenve of an' *inter-mediate mechanism”between polar mechanism and electron transter mechanism acording to Pros Shaik“Curve CrossingModel" . The reduction of 9-flurenylideneralonnitrile with BNAH proceeded through electron lransfer and the intermne-diacy of a carbanion with negative charge on C-9 of fluorenyl nucleus and showed a kinetie H/D istope efet of2.6.Further researh work is in progress.Key words NADH model, electron lransfer, curve crossing model■Received 2001-07-13; Aceped 2001-08-30.國家自然科學(xué)基金(Nos.29392201, 29672031, 29832040)資 助項目。.第11期劉有成等:輔酶NADH模型物還原活化烯烴反應(yīng)機理研究1前言1,4-”“氫煙酰胺腺嘌呤二核背酸(NADH)是--應(yīng)則是按電子轉(zhuǎn)移、脫溴、奪氫機理進(jìn)行的(Scheme個典型的輔酶,它在生物氧化-還原反應(yīng)中起著重1)。要的作用。有關(guān)NADH如何轉(zhuǎn)移形式上的一一個負(fù)氫給反應(yīng)底物的問題-直是令人感興趣的課題,大部Hy