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nbm110

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[求助] （有机化学）老哥们继续来翻译啊~~我又发帖了 哈哈~~

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).
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金虫 (正式写手)

【答案】应助回帖

nbm110(金币+100, 翻译EPI+1): ★★★★★最佳答案 okok多谢哈~~金币给你~ 2012-02-10 11:44:23
不好意思，昨天去走亲戚了，今天起了大早，翻译完了，你参考下：
利用多米诺骨牌式反应合成2-乙炔基苯胺/环化。实验的过程中发现芳基碘化物可以同1-炔基可以通过铜催化反应产生耦合产物，从而引发一个多米诺骨牌式的炔基苯胺/环化得过程，而在该具体的反应中，可以用2-碘三氟乙酰苯胺和末端炔通过一步直接制备物N-H的2-芳基和2-杂环哚吲，从而避免了需要分离2-炔基三氟乙酰苯胺中间体的麻烦（路线1，断开a+c）。该反应的具体化学反应路线7的实例如下：使用溶于甲苯或者二恶烷中的[Cu(phen](PPh3)2]NO3 和CuI/PPh3作为有效的催化体系。该反应可以同许多的末端炔反应，包括含有醚，酰胺，醛，酯，硝基，杂环基团的末端炔。在炔烃中，只研究了1-己炔，用1-己炔值得了理想的哚吲，但是产率不是很高，同样是因为缓慢的耦合步骤。使用同样的工艺，成功制备了2-芳基和2-杂芳基吡咯并[2,3-b]喹喔啉，具体的过程如下：将末端炔与2-溴-3-三氟乙酰氨基喹啉反应，催化体系是uI，PPh3，和K2CO3，溶剂是二恶烷，温度是110℃。该多米诺骨牌式的耦合/环化过程同样可以用以下的催化体系实现，将1,10 - 菲罗啉固定在聚苯乙烯/二乙烯基苯固体基材上，并由Cu(PPh3)NO3充当铜元素的提供物。使用[Cu(phen)(PPh3)2]NO3时，环化步骤效率并不是很高。在耦合中间体和2取代哚吲之间，产物比较倾向于生成第一个。然而，催化体系可以重复使用3次。该过程随后被扩展到2-溴炔基三氟乙酰苯胺，使用CuI和脯氨酸作为配体（路线7）。

非常显著的是，尽管使用了少量的溴衍生物，但相对于2-碘三氟乙酰苯胺，氨基酸配体可以使反应在更为温和的条件下进行。同于2-碘三氟乙酰苯胺反应相似的是，使用庚炔和2-溴炔基三氟乙酰苯胺反应，反应的产率较低。然而，当向体系内加入氧保护炔醇时，哚吲的产率非常令人满意。比较可能的原因是，末端炔的电子云密度的微小变化对耦合步骤起到影响作用。2-炔基苯胺被成功制备出来，并进行了环化以制备相应的哚吲。2-炔基苯胺的制备过程如下：使用非常容易得到的N-保护乙炔苯胺同多聚甲醛和二级胺在CuBr存在的条件下反应（路线1，将a+d+e分开看）。该三部分的反应提供了一个非常容易制备2-（甲胺）哚吲的方法，并且该三部分反应被合理地分为一个多米诺过程，首先是乙炔铜与亚胺离子发生一个曼奇尼反应，然后是铜催化的氢胺化反应，具体为铜催化2-炔基苯胺中间体（路线9）。

使用较为适当的取代胺结合铜催化的环化和随后的环化步骤，本工艺路线被证明可以用来合成多种多环芳烃吲哚衍生物。哚吲苯并-1,4-二氮杂草被成功地合成了出来，通过微波引发2- 乙炔苯胺和邻溴苄胺反应并经过铜催化的多米诺式的三组分耦合/哚吲生成N-芳基化产物（路线10）。该方法可以被扩展到制备吡啶-和噻吩四环化合物。1,2,3,4-四氢-β喹啉被成功制备出来，同时其产率处于中等至较好的状态。具体的过程如下：使用铜催化的三组分耦合/环化，具体为乙炔苯胺，醛和一种二级胺，然后使用KOBu-t/正己烷或者MsOH处理哚吲中间体。

从二乙炔氨基衍生物1开始，通过该三部分的化学反应过程（路线12a），分子内氢胺化反应（路线12b）和随后的分子内氢胺化/三部分耦合-环化反应（路线12c），许多稠吡咯-吲哚被成功地合成出来。

2-环芳炔的N-芳基化过程为制备2-炔基苯胺提供了一个很有参考价值的选择方案。并且该过程已经被成功用于多米诺式式的N-芳基化/氢胺化过程（路线1，将a+b分开看）。在该过程中，2-环芳炔经历了铜催化的N-芳基化过程，具体是同苯胺，酰胺和氨基甲酸酯类反应，接着是铜催化的环化过程已制备相应的哚吲衍生物（路线13）。

N-芳基哚吲的合成可以在没有配体的条件下制备。相对于NaOBu-t或者LiOBu-t，KOBu-t对于相应的基体效果更好。正取代物或者具有空间位阻的胺类也可以用于本反应。合成N-芳基哚吲的最佳工艺条件可以从合成5-氮杂哚吲的反应中看出。利用该工艺条件的特点，可以用一锅反应就制备无N-H的哚吲，具体是在铜催化的多米诺式N-芳基/氢胺化转变中，使用叔丁基氨基甲酸酯作为亲核试剂，并用三氟乙酸进行简单处理。芳基炔中的碳碳三键上含有一个正取代的氮，是一个亲核试剂。同样也是在Pd(PPh3)4和CuCl双金属催化剂作用下由2-炔基苯基异氰酸酯和烯丙基碳酸盐制备的。利用该反应，一系列的2-炔基 苯基异氰酸酯成功转化为相应的3-烯丙基-N（烷氧羰基）哚吲（路线1，将a+f连在一起）。一些环化反应的事例见路线14.CuCl被证明是非常有效的催化剂，使用CuCl时产率比CuBr要高，而且远比其它的铜盐有效，诸如CuI, Cu(OAc), (CuOTf)2•benzene, and CuCl2。当位于炔基残基（R1）的取代基体积较大时，需要更长的反应时间。当取代基为叔丁基时，没有烯丙基哚吲产物，而且产物唯一，是相应的N-烯丙基苯胺衍生物。苯环上的对位取代的电子效应和烯丙基碳酸盐R2取代基的体积效应对反应结果的影响不是很大。可能的反应机理包含以下几步：a）异氰酸酯同P-烯丙基醇钯反应生成P-烯丙基钯络合物2并与3处于一个平衡状态（最有可能的是含有杂化原子的二-p-烯丙基钯同系物4）；b）反式金属化过程，生成中间体5；c）发生一个反式胺钯化转变；d）发生一个还愿消除反应（路线15）。
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