按Lehn的定义, 超分子化学就是"分子组装和分子间键的化学 chemistry beyond the molecule".它是研究超分子或分子超结构的形成,性质及应用的化学,包括 分子识别原理,受体化学,分子自组装,超分子光化学,超分子电化学,超分子催化化学,超分子工程学,超分子生命科学等.
一句话，研究涉及分子减弱作用的朋友欢迎来看看
『一周一水』2008.3.19－3.27【C——N键的构建】
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『一周一水』的解释：
水区缺水,看到学术交流区有[一周一题]的几个帖子,不错的想法,东施效颦一下,在水区也开展个[一周一水]专题,一来为增加水区水资源,二来让更多得人了解个多的化学基础知识(因为是基础,所以只敢在水区
),三来鼓励大家多多参与,只有参与才会让我们进步,四来给大家借机给点银子
.
对于专业范围局限较大的文献讨论等,水区的水题则更基础,更具普遍的参与性.这样大多数人（虽然我们有很多的QM，但我们有更多的NQM）就可以参与进来，这并不是鼓励大家只灌水，不进步，相反，更鼓励大家到专业交流区发帖。
让学术交流区展示chem8的高,让化学水吧展示chem8的博.
请大家参与进来吧
有你,有我,有大家,chem8才会更精彩
鼓励广大会员在新的一周开始时加上自己感兴趣的题目
2.jpg
http://www.organic-chemistry.org/synthesis/C2N/nitriles.shtm
http://www.organic-chemistry.org/synthesis/C3N/nitriles.shtm
===============================
其他一周一水相关主题：
[本帖最后由 cc136520 于 2008-3-19 21:46 编辑]
水区缺水,看到学术交流区有[一周一题]的几个帖子,不错的想法,东施效颦一下,在水区也开展个[一周一水]专题,一来为增加水区水资源,二来让更多得人了解个多的化学基础知识(因为是基础,所以只敢在水区
),三来鼓励大家多多参与,只有参与才会让我们进步,四来给大家借机给点银子.对于专业范围局限较大的文献讨论等,水区的水题则更基础,更具普遍的参与性.这样大多数人（虽然我们有很多的QM，但我们有更多的NQM）就可以参与进来，这并不是鼓励大家只灌水，不进步，相反，更鼓励大家到专业交流区发帖。
让学术交流区展示chem8的高,让化学水吧展示chem8的博.
请大家参与进来吧
有你,有我,有大家,chem8才会更精彩
鼓励广大会员在新的一周开始时加上自己感兴趣的题目
================================================
本周主题: C-N Bond Formation
================================================
如题，本期主题涉及C—N，C=N 及CN叁键的构建，旨在复习有机合成化学的基础知识，顺便拓宽大家的知识结构。
参与注意事项：
1.以图例形式给出构建的反应详细信息
2.提供全文链接或者其他相关信息
3.如果你做过这个反应，请说说你的感受，体会！
＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝
http://www.organic-chemistry.org/synthesis/C1N/index.shtm
2.jpg
http://www.organic-chemistry.org/synthesis/C2N/nitriles.shtm
http://www.organic-chemistry.org/synthesis/C3N/nitriles.shtm
===============================
其他一周一水相关主题：
[本帖最后由 cc136520 于 2008-3-19 21:46 编辑]
TAG:
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zjinan发布于2008-03-19 22:06:26
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给出的都是精华！！！！！！！！！！！！谢谢！！
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cc136520 发布于2008-03-19 22:08:42
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Gabriel Synthesis
Potassium phthalimide is a -NH2-synthon which allows the preparation of primary amines by reaction with alkyl halides. After alkylation, the phthalimid is not nucleophile and does not react anymore. Product is cleaved by reaction with base or hydrazine, which leads to a stable cyclic product.
Mechanism
Note: Phthalimide is acidic!
Cleavage:
[attach]5853[/attach]
Recent Literature
Organic Reactions in Ionic liquids: N-Alkylation of Phthalimide and Several Nitrogen Heterocycles
Z.-G. Le, Z.-C. Chen, Y. Hu, Q.-G. Zheng, Synthesis, 2004, 208-212.
A convenient Two-Step Procedure for the Synthesis of Substituted Allylic Amines from Allylic Alcohols
S. E. Sen, S. L. Roach, Synthesis, 1995, 756-758
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Curtius Rearrangement
The Curtius Rearrangement is the thermal decomposition of carboxylic azides to produce an isocyanate. These intermediates may be isolated, or their corresponding reaction or hydrolysis products may be obtained.
The reaction sequence - including subsequent reaction with water which leads to amines - is named the Curtius Reaction. This reaction is similar to the Schmidt Reaction with acids, differing in that the acyl azide in the present case is prepared from the acyl halide and an azide salt.
Mechanism
Preparation of azides:
Decomposition:
Reaction with water to the unstable carbamic acid derivative which will undergo spontaneous decarboxylation:
Isocyanates are versatile starting materials:
Isocyanates are also of high interest as monomers for polymerization work and in the derivatisation of biomacromolecules.
Recent Literature
Boc-Protected Amines via a Mild and Efficient One-Pot Curtius Rearrangement
H. Lebel, O. Leogane, Org. Lett., 2005, 7, 4107-4110.
Radical Azidonation of Aldehydes
L. Marinescu, J. Thinggaard, I. B. Thomsen, M. Bols, J. Org. Chem., 2003, 68, 9453-9455.
Radical Azidonation of Aldehydes
L. Marinescu, J. Thinggaard, I. B. Thomsen, M. Bols, J. Org. Chem., 2003, 68, 9453-9455.
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Delépine Reaction
The Delépine Reaction allows the synthesis of primary amines from alkyl halides by the reaction with hexamethylentetramine (urotropine) and subsequent acidic hydrolysis of the resulting quartenary ammonium salt.
Mechanism
An SN2 reaction leads to the hexamethylentetramine salt. In chloroform, the starting materials are soluble wheareas the products crystallize out. It is usually not possible to purify the salt:
Hexamethylenetetramine is formed in nearly quantitative yield from the condensation of ammonia and formaldehyde.
The compound is rather stable, although dihetero-substituted methylene groups are usually highly reactive. In neutral, aqueous solution, urotropine remains stable even at elevated temperatures. Urotropine decomposes in dilute aqueous acid, and the derived ammonium salts also decompose to form the amine hydrochloride and formaldehyde (and formaldehyde diethylacetal):
During acidic hydrolysis or ethanolysis, semiaminals are formed first; these further decompose to yield formaldehyde or the diethylacetal, ammonium salt and the amine hydrochloride:
For a review of the uses of hexamethylenetetramine, a versatile reagent in organic synthesis, please refer to Blažević (Synthesis, 1979, 161-176. DOI).
Recent Literature
A Convenient Route to 3-Pyrroline Utilizing the Delépine Reaction
S. Brandänge, B. Rodriquez, Synthesis, 1988, 347-348.
Reactions of alkyl (halomethyl)furancarboxylates with hexamethylenetetramine
I. M. Lapina, L. M. Pevzner, A. A. Potekhin, Russ. J. Gen. Chem., 2006, 1304-1309.
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Mitsunobu Reaction
The Mitsunobu Reaction allows the conversion of primary and secondary alcohols to esters, phenyl ethers, thioethers and various other compounds. The nucleophile employed should be acidic, since one of the reagents (DEAD, diethylazodicarboxylate) must be protonated during the course of the reaction to prevent from side reactions.
Suitable nitrogen nucleophiles include phthalimide or hydrogen azide; subsequent hydrolysis (in the case of using phthalimide, see Gabriel Synthesis) or selective reduction (in the case of azide formation, see Staudinger Reaction) makes the corresponding amines accessible.
Mechanism
The triphenylphosphine combines with DEAD to generate a phosphonium intermediate that binds to the alcohol oxygen, activating it as a leaving group. Substitution by the carboxylate, mercaptyl, or other nucleophile completes the process.
The reaction proceeds with clean inversion, which makes the Mitsunobu Reaction with secondary alcohols a powerful method for the inversion of stereogenic centers in natural product synthesis.
Side Reaction:
New protocols have been developed which allow better removal of side products and/or the conversion of more basic nucleophiles.
Recent Literature
Simplification of the Mitsunobu Reaction. Di-p-chlorobenzyl Azodicarboxylate: A New Azodicarboxylate
B. H. Lipshutz, D. W. Chung, B. Rich, R. Corral, Org. Lett., 2006, 8, 5069-5072.
Fluorous Mitsunobu reagents and reactions
S. Dandapani, D. P. Curran, Tetrahedron, 2002, 58, 3855-3864.
A convenient Two-Step Procedure for the Synthesis of Substituted Allylic Amines from Allylic Alcohols
S. E. Sen, S. L. Roach, Synthesis, 1995, 756-758.
Use of Sonication for the Coupling of Sterically Hindered Substrates in the Phenolic Mitsunobu Reaction
S. D. Lepore, Y. He, J. Org. Chem., 2003, 68, 8261-8263.
Organocatalytic Mitsunobu Reactions
T. Y. S. But, P. H. Toy, J. Am. Chem. Soc., 2006, 128, 9636-9637.
Carbon Nucleophiles in the Mitsunobu Reaction. Mono and Dialkylation of Bis(2,2,2-trifluorethyl) Malonates
J. M. Takacs, Z. Xu, X.-T. Jiang, A. P. Leonov, G. C. Theriot, Org. Lett., 2002, 4, 3843-3845.
Synthesis of N-H vinylaziridines: a comparative study
B. Olofsson, R. Wijtmans, P. Somfai, Tetrahedron, 2002, 58, 5979-5982.
Exploration of the Mitsunobu Reaction with Tosyl- and Boc-Hydrazones as Nucleophilic Agents
J. M. Keith, L. Gomez, J. Org. Chem., 2006, 71, 7113-7116.
Conversion of Alcohols, Thiols, Carboxylic Acids, Trimethylsilyl Ethers, and Carboxylates to Thiocyanates with Triphenylphosphine/Diethylazodicarboxylate/NH4SCN
N. Iranpoor, H. Firouzabadi, B. Akhlaghinia, R. Azadi, Synthesis, 2004, 92-96.
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Staudinger Reduction
Azides may be converted to amines by hydrogenation, but another possibility is the Staudinger Reaction, which is a very mild azide reduction. As there are a variety of methods for preparing azides readily, the Staudinger Reaction makes it possible to use -N3 as an -NH2 synthon.
Mechanism
Triphenylphosphine reacts with the azide to generate a phosphazide, which loses N2 to form an iminophosphorane. Aqueous work up leads to the amine and the very stable phosphine oxide.
W. Q. Tian, Y. A. Wang, J. Org. Chem. 2004, 69, 4299. DOI
F. L. Lin, H. M. Hoyt, H. v. Halbeek, R. G. Bergman, C. R. Bertozzi, J. Am. Chem. Soc, 2005, 127, 2686. DOI
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Schmidt Reaction
The acid-catalysed reaction of hydrogen azide with electrophiles, such as carbonyl compounds, tertiary alcohols or alkenes. After a rearrangement and extrusion of N2, amines, nitriles, amides or imines are produced.
Mechanism
Reaction of carboxylic acids gives acyl azides, which rearrange to isocyanates, and these may be hydrolyzed to carbamic acid or solvolysed to carbamates. Decarboxylation leads to amines.
The reaction with a ketone gives an azidohydrin intermediate, which rearranges to form an amide:
Alkenes are able to undergo addition of HN3 as with any HX reagent, and the resulting alkyl azide can rearrange to form an imine:
Tertiary alcohols give substitution by azide via a carbenium ion, and the resulting alkyl azide can rearrange to form an imine.
Recent Literature
Gold(I)-Catalyzed Intramolecular Acetylenic Schmidt Reaction
D. J. Gorin, N. R. Davis, F. D. Toste, J. Am. Chem. Soc., 2005, 127, 11260-11261.
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An efficient, general procedure for highly chemoselective reductive mono-alkylation of ammonia with ketones is reported. Treatment of ketones with ammonia in ethanol and titanium(IV) isopropoxide, followed by in situ reduction with sodium borohydride, and a simple workup afforded primary amines in good to excellent yields. Reductive alkylation of ammonia with aldehydes, on the other hand, afforded the corresponding symmetrical secondary amines selectively.
B. Miriyala, S. Bhattacharyya, J. S. Williamson, Tetrahedron, 2004, 60, 1463-1471.
The synthesis of free α-chiral amines by a one-pot multicomponent procedure involves the formation of N-diphenylphosphinoylimines from commercially available starting materials and the subsequent enantioselective addition of diakylzinc reagents using an air-stable precatalyst complex.
. Cote, A. B. Charette, J. Org. Chem., 2005, 70, 10864-10867.
The electrophilic amination of Grignard reagents with 4,4,5,5-tetramethyl-1,3-dioxolan-2-one O-phenylsulfonyloxime followed by acidic hydrolysis of the resulting imines gave primary amines.
M. Kitamura, T. Suga, S. Chiba, K. Narasaka, Org. Lett., 2004, 6, 4619-4621.[/td]
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http://www.organic-chemistry.org/namedreactions/eschweiler-clarke-reaction.shtm
Eschweiler-Clarke Reaction
This reaction allows the preparation of tertiary methylamines from secondary amines via treatment with formaldehyde in the presence of formic acid. The formate anion acts as hydride donor to reduce the imine or iminium salt, so that the overall process is a reductive amination. The formation of quaternary amines is not possible.
Mechanism
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合成大师Buchwald 关于C－N键合成的报告
Stephen_L_Buchwald.part1.rar
(2008-03-23 19:47:19, Size: 838 KB, Downloads: 28)Stephen_L_Buchwald.part2.rar
(2008-03-23 19:47:19, Size: 838 KB, Downloads: 19)Stephen_L_Buchwald.part3.rar
(2008-03-23 19:47:19, Size: 151 KB, Downloads: 18)
