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nbm110金蟲 (小有名氣)
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[求助]
（有機化學）老哥們繼續(xù)來翻譯啊~~我又發(fā)帖了 哈哈~~
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Domino synthesis of 2-alkynylanilid(n)es/cyclization. The ob- servation that aryl iodides and 1-alkynes can give coupling prod- ucts through copper-catalyzed reactions21 set the stage to the devel-opment of a domino alkynylation/cyclization process in which free N–H2-aryl- and 2-heteroarylindoles are directly prepared from2- iodotrifluoroacetanilides and terminal alkynes in a single operative step, avoiding the isolation of the 2-alkynyltrifluoroacetanilide intermediates (Scheme 1, disconnection a + c). An example of this chemistry is shown in Scheme 7. Both [Cu(phen](PPh3)2]NO3 and CuI/PPh3 in toluene or dioxane serve as efficient catalysts. The reaction tolerates a wide range of functionalized terminal alkynes, including those containing ether, amide, aldehyde, ester, nitro, and heterocyclic groups. Only 1-hexyne, among the alkynes that were investigated, produced the desired indole product in low yield, very likely because of a sluggish coupling step. Using the same strategy, 2-aryl- and 2-heteroaryl pyrrolo[2,3-b]quinoxalines have been prepared through the reaction of terminal alkynes with 2-bromo-3-trifluoroacetamidoquinoxaline in the presence of catalytic amounts of CuI, PPh3 and K2CO3 in dioxane at 110 ◦C. This domino copper-catalyzed coupling/cyclization process was also performed using a catalytic system made of a 1,10- phenanthroline immobilized on a polystyrene/divinylbenzene solid support and Cu(PPh3)NO3 as the copper source. The cyclization stepwas not as efficient aswith [Cu(phen)(PPh3)2]NO3. The ratio between the coupling intermediate and the 2-substituted indole was slightly skewed toward the first one. However, the catalytic system could be reused three times. The procedure has been subsequently extended to 2- bromoalkynyltrifluoroacetanilides using CuI and L-proline as the ligand (Scheme 7). Notably, despite the employment of the less reactive bromo derivatives, the amino acid ligand al- lows for running the reaction under conditions milder than those employed with 2-iodotrifluoroacetanilides. Analogously to the related reaction with 2-iodotrifluoroacetanilide, treatment of 2-bromotrifluoroacetanilide with 1-heptyne produced 2-n- pentylindole in low yield. However, when O-protected propargyl alcohols were employed, the desired indoles were obtained in satisfactory yields. Most probably, subtle changes in the electron density of the terminal alkynes can influence their reactivity in the coupling step. 2-Alkynylanilides have been prepared and cyclized in situ to indoles by treating readily available N-protected ethynylanilines with paraformaldehyde and secondary amines in the presence of CuBr (Scheme 1, disconnection a + d + e). This three-component reaction provides a facile access to 2-(aminomethyl)indoles (Scheme 8) and has been rationalized in terms of a domino process that involves a Mannich type reaction of copper acetylides with iminium ions followed by a copper-catalyzed hydroamination of the resultant 2-alkynylanilide intermediates (Scheme 9). With properly substituted amines, this strategy has been shown to be feasible for the synthesis of a variety of polycyclic indole derivatives combining the copper-catalyzed cyclization with a subsequent cyclization step. Indole-fused benzo-1,4-diazepines have been prepared by a copper-catalyzed domino three-component coupling/indole formation/N-arylation sequence undermicrowave irradiation starting from2-ethynylanilines and o- bromobenzylamines (Scheme 10). The reaction can be extended to the preparation of pyridine- and thiophene-fused tetracyclic compounds. 1,2,3,4-Tetrahydro-b-carbolines have been prepared in moderate to good yields by copper-catalyzed domino three- component coupling/cyclization of an appropriate ethynylaniline, aldehyde, and a secondary amine followed by the cyclization of the resultant indole intermediate upon treatment with KOBu- t/hexane or MsOH (Scheme 11). Starting from diethynyl, diamino derivatives 1, various pyrrole- fused indoles have been prepared via the three component chem- istry (Scheme 12a), intramolecular hydroamination (Scheme 12b) and a sequential intramolecular hydroamination/three compo- nent coupling-cyclization reaction (Scheme 12c). The N-arylation of 2-haloarylalkynes represents an interesting alternative for generating 2-alkynylanilid(n)es in situ.Thisstrategy has been successfully employed in the development of a domino N-arylation/hydroamin(d)ation process (Scheme 1, disconnection a + b). In this process 2-haloarylalkynes undergo a copper- catalyzed N-arylation with anilines, amides and carbamates followed by a copper-catalyzed cyclization in situ to the corre- sponding indole derivatives (Scheme 13). The synthesis of N- arylindoles was performed under ligand-free conditions. KOBu-t is superior to related bases such as NaOBu-t or LiOBu-t. ortho- Substituents ormore sterically hindered anilines arewell tolerated. The optimized protocol for the synthesis ofN-acylindoles has been shown to be applicable to the synthesis of 5-azaindoles. Taking ad- vantage of this protocol, freeN–Hindoles can be prepared through a one-pot process by using tert-butylcarbamate as nucleophile in the copper-catalyzed domino N-arylation/hydroamin(d)ation transformation, along with a subsequent simple treatment with trifluoroacetic acid. Arylalkynes bearing a nitrogen nucleophile ortho to the arbon–carbon triple bond have also been generated from 2- alkynyl)phenylisocyanates and allyl carbonates in the presence f Pd(PPh3)4 and CuCl bimetallic catalyst. Using this reaction, a ariety of 2-(alkynyl)phenylisocyanates have been converted into he corresponding 3-allyl-N-(alkoxycarbonyl)indoles (Scheme 1, isconnection a + f ). Some examples of this cyclization reaction re shown in Scheme 14. CuCl was proved to give higher yields han CuBr and to be far superior to other copper salts such as CuI, Cu(OAc), (CuOTf)2·benzene, and CuCl2. Longer reaction times are required when the substituent on the alkyne fragment (R1 ) is a bulky substituent. With a tert-butyl group no allylindole was obtained and the sole product was the corresponding N- allylaniline derivative. Electronic effects of the para substituents on the aromatic ring as well as the bulkiness of the substituents R2 of the allyl carbonates do not seem to exert a significant influence on the reaction outcome. The proposed mechanism involves the following basic steps: a) the reaction of the isocyanate group with the p-allylpalladium alkoxide complex to give the p-allylpalladium complex 2 in equilibrium with 3 (most probably, it could be better represented as a heteroatom-containing bis-p-allylpalladium analogue 4); b) a transmetalation step generating the intermediate 5;c)a trans-aminopalladation followed by d) a reductive elimination (Scheme 15). 比較長 給你100金幣~~~ |
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小劉淵
金蟲 (正式寫手)
- 翻譯EPI: 9
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【答案】應助回帖
nbm110(金幣+100, 翻譯EPI+1): ★★★★★最佳答案 okok多謝哈~~金幣給你~ 2012-02-10 11:44:23
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不好意思，昨天去走親戚了，今天起了大早，翻譯完了，你參考下： 利用多米諾骨牌式反應合成2-乙炔基苯胺/環(huán)化。實驗的過程中發(fā)現(xiàn)芳基碘化物可以同1-炔基可以通過銅催化反應產(chǎn)生耦合產(chǎn)物，從而引發(fā)一個多米諾骨牌式的炔基苯胺/環(huán)化得過程，而在該具體的反應中，可以用2-碘三氟乙酰苯胺和末端炔通過一步直接制備物N-H的2-芳基和2-雜環(huán)哚吲，從而避免了需要分離2-炔基三氟乙酰苯胺中間體的麻煩（路線1，斷開a+c）。該反應的具體化學反應路線7的實例如下：使用溶于甲苯或者二惡烷中的[Cu(phen](PPh3)2]NO3 和CuI/PPh3作為有效的催化體系。該反應可以同許多的末端炔反應，包括含有醚，酰胺，醛，酯，硝基，雜環(huán)基團的末端炔。在炔烴中，只研究了1-己炔，用1-己炔值得了理想的哚吲，但是產(chǎn)率不是很高，同樣是因為緩慢的耦合步驟。使用同樣的工藝，成功制備了2-芳基和2-雜芳基吡咯并[2,3-b]喹喔啉，具體的過程如下：將末端炔與2-溴-3-三氟乙酰氨基喹啉反應，催化體系是uI，PPh3，和K2CO3，溶劑是二惡烷，溫度是110℃。該多米諾骨牌式的耦合/環(huán)化過程同樣可以用以下的催化體系實現(xiàn)，將1,10 - 菲羅啉固定在聚苯乙烯/二乙烯基苯固體基材上，并由Cu(PPh3)NO3充當銅元素的提供物。使用[Cu(phen)(PPh3)2]NO3時，環(huán)化步驟效率并不是很高。在耦合中間體和2取代哚吲之間，產(chǎn)物比較傾向于生成第一個。然而，催化體系可以重復使用3次。該過程隨后被擴展到2-溴炔基三氟乙酰苯胺，使用CuI和脯氨酸作為配體（路線7）。 非常顯著的是，盡管使用了少量的溴衍生物，但相對于2-碘三氟乙酰苯胺，氨基酸配體可以使反應在更為溫和的條件下進行。同于2-碘三氟乙酰苯胺反應相似的是，使用庚炔和2-溴炔基三氟乙酰苯胺反應，反應的產(chǎn)率較低。然而，當向體系內(nèi)加入氧保護炔醇時，哚吲的產(chǎn)率非常令人滿意。比較可能的原因是，末端炔的電子云密度的微小變化對耦合步驟起到影響作用。2-炔基苯胺被成功制備出來，并進行了環(huán)化以制備相應的哚吲。2-炔基苯胺的制備過程如下：使用非常容易得到的N-保護乙炔苯胺同多聚甲醛和二級胺在CuBr存在的條件下反應（路線1，將a+d+e分開看）。該三部分的反應提供了一個非常容易制備2-（甲胺）哚吲的方法，并且該三部分反應被合理地分為一個多米諾過程，首先是乙炔銅與亞胺離子發(fā)生一個曼奇尼反應，然后是銅催化的氫胺化反應，具體為銅催化2-炔基苯胺中間體（路線9）。 使用較為適當?shù)娜〈方Y合銅催化的環(huán)化和隨后的環(huán)化步驟，本工藝路線被證明可以用來合成多種多環(huán)芳烴吲哚衍生物。哚吲苯并-1,4-二氮雜草被成功地合成了出來，通過微波引發(fā)2- 乙炔苯胺和鄰溴芐胺反應并經(jīng)過銅催化的多米諾式的三組分耦合/哚吲生成N-芳基化產(chǎn)物（路線10）。該方法可以被擴展到制備吡啶-和噻吩四環(huán)化合物。1,2,3,4-四氫-β喹啉被成功制備出來，同時其產(chǎn)率處于中等至較好的狀態(tài)。具體的過程如下：使用銅催化的三組分耦合/環(huán)化，具體為乙炔苯胺，醛和一種二級胺，然后使用KOBu-t/正己烷或者MsOH處理哚吲中間體。 從二乙炔氨基衍生物1開始，通過該三部分的化學反應過程（路線12a），分子內(nèi)氫胺化反應（路線12b）和隨后的分子內(nèi)氫胺化/三部分耦合-環(huán)化反應（路線12c），許多稠吡咯-吲哚被成功地合成出來。 2-環(huán)芳炔的N-芳基化過程為制備2-炔基苯胺提供了一個很有參考價值的選擇方案。并且該過程已經(jīng)被成功用于多米諾式式的N-芳基化/氫胺化過程（路線1，將a+b分開看）。在該過程中，2-環(huán)芳炔經(jīng)歷了銅催化的N-芳基化過程，具體是同苯胺，酰胺和氨基甲酸酯類反應，接著是銅催化的環(huán)化過程已制備相應的哚吲衍生物（路線13）。 N-芳基哚吲的合成可以在沒有配體的條件下制備。相對于NaOBu-t或者LiOBu-t，KOBu-t對于相應的基體效果更好。正取代物或者具有空間位阻的胺類也可以用于本反應。合成N-芳基哚吲的最佳工藝條件可以從合成5-氮雜哚吲的反應中看出。利用該工藝條件的特點，可以用一鍋反應就制備無N-H的哚吲，具體是在銅催化的多米諾式N-芳基/氫胺化轉變中，使用叔丁基氨基甲酸酯作為親核試劑，并用三氟乙酸進行簡單處理。芳基炔中的碳碳三鍵上含有一個正取代的氮，是一個親核試劑。同樣也是在Pd(PPh3)4和CuCl雙金屬催化劑作用下由2-炔基苯基異氰酸酯和烯丙基碳酸鹽制備的。利用該反應，一系列的2-炔基 苯基異氰酸酯成功轉化為相應的3-烯丙基-N（烷氧羰基）哚吲（路線1，將a+f連在一起）。一些環(huán)化反應的事例見路線14.CuCl被證明是非常有效的催化劑，使用CuCl時產(chǎn)率比CuBr要高，而且遠比其它的銅鹽有效，諸如CuI, Cu(OAc), (CuOTf)2•benzene, and CuCl2。當位于炔基殘基（R1）的取代基體積較大時，需要更長的反應時間。當取代基為叔丁基時，沒有烯丙基哚吲產(chǎn)物，而且產(chǎn)物唯一，是相應的N-烯丙基苯胺衍生物。苯環(huán)上的對位取代的電子效應和烯丙基碳酸鹽R2取代基的體積效應對反應結果的影響不是很大�？赡艿姆磻獧C理包含以下幾步：a）異氰酸酯同P-烯丙基醇鈀反應生成P-烯丙基鈀絡合物2并與3處于一個平衡狀態(tài)（最有可能的是含有雜化原子的二-p-烯丙基鈀同系物4）；b）反式金屬化過程，生成中間體5；c）發(fā)生一個反式胺鈀化轉變；d）發(fā)生一個還愿消除反應（路線15）。 |
2樓2012-02-10 11:14:52
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