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Synthesis of Allenes via Palladium-Catalyzed Hydrogen-Transfer Reactions: Propargylic Amines as an Allenyl Anion Equivalent
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Abstract
Synthesis of allenes has been achieved by using palladium-catalyzed hydrogen-transfer reactions. Various propargylic amines, which were readily prepapred from iodobenzenes and propargylic amines by Sonogashira coupling reaction, underwent the hydrogen-transfer reaction in the presence of Pd2dba3·CHCl3/(C6F5)3P catalyst at 100 °C in dioxane for 24 h, giving the corresponding allenes in 43−99% yields. Various propargylic alcohols containing a propargylic aminomethyl group, synthesized by the addition of lithium acetylides of N,N-diisopropylprop-2-ynylamine to aldehydes and a ketone, also underwent the hydrogen-transfer reaction in the presence of Pd2dba3·CHCl3 catalyst and (C6F5)3P at 80 °C in dioxane, giving the corresponding allenes in 56−92% yields. In the current transformation, propargylic amines can be handled as an allenyl anion equivalent and introduced into various electrophiles to be transformed into allenes under palladium-catalyzed conditions.
Citing Articles
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This article has been cited by 14 ACS Journal articles (5 most recent appear below).
Copper(I)-Catalyzed Substitution Reactions of Propargylic Amines: Importance of C(sp)−C(sp3) Bond Cleavage in Generation of Iminium Intermediates
Tsuyuka Sugiishi, Akifumi Kimura and Hiroyuki NakamuraJournal of the American Chemical Society2010 132 (15), 5332-5333Copper(I)-Catalyzed Substitution Reactions of Propargylic Amines: Importance of C(sp)−C(sp3) Bond Cleavage in Generation of Iminium Intermediates
Tsuyuka Sugiishi, Akifumi Kimura and Hiroyuki NakamuraJournal of the American Chemical Society2010 132 (15), 5332-5333Substitution reactions of propargylic amines proceed in the presence of copper(I) catalysts. Mechanistic studies showed that C(sp)−C(sp3) bond cleavage assisted by nitrogen lone-pair electrons is essential for the reaction, and the resulting iminium ...
One-Pot Synthesis of 1,3-Disubstituted Allenes from 1-Alkynes, Aldehydes, and Morpholine
Jinqiang Kuang and Shengming MaJournal of the American Chemical Society2010 132 (6), 1786-1787One-Pot Synthesis of 1,3-Disubstituted Allenes from 1-Alkynes, Aldehydes, and Morpholine
Jinqiang Kuang and Shengming MaJournal of the American Chemical Society2010 132 (6), 1786-1787ZnI2 has been identified as the catalyst for the one-step synthesis of allenes from terminal alkynes and aldehydes with morpholine as the base in toluene. The reaction is believed to proceed via the intermediacy of propargylic amines, which was converted ...
Generation of Allenic/Propargylic Zirconium Complexes and Subsequent Cross-Coupling Reactions: A Facile Synthesis of Multisubstituted Allenes
Hao Zhang, Xiaoping Fu, Jingjin Chen, Erjuan Wang, Yuanhong Liu and Yuxue LiThe Journal of Organic Chemistry2009 74 (24), 9351-9358Generation of Allenic/Propargylic Zirconium Complexes and Subsequent Cross-Coupling Reactions: A Facile Synthesis of Multisubstituted Allenes
Hao Zhang, Xiaoping Fu, Jingjin Chen, Erjuan Wang, Yuanhong Liu and Yuxue LiThe Journal of Organic Chemistry2009 74 (24), 9351-9358The β-alkoxide elimination reaction of propargylic ether with Negishi reagent leads to allenes and/or alkynes after hydrolysis. The product distribution is highly dependent on the substitution pattern of starting propargylic ethers; that is, aryl- or ...
Synthesis and Characterization of Conjugated Diallenes and Their Binuclear Ruthenium η3-Allyl Complexes
Jian-Long Xia, Xianghua Wu, Yinghui Lu, Gang Chen, Shan Jin, Guang-ao Yu and Sheng Hua LiuOrganometallics2009 28 (9), 2701-2706Synthesis and Characterization of Conjugated Diallenes and Their Binuclear Ruthenium η3-Allyl Complexes
Jian-Long Xia, Xianghua Wu, Yinghui Lu, Gang Chen, Shan Jin, Guang-ao Yu and Sheng Hua LiuOrganometallics2009 28 (9), 2701-2706A series of binuclear ruthenium η3-allyl complexes [(PPh3)2(CO)ClRu]2[(η3-CH2CHCH)2R] (R = 1,4-C6H4, 4,4′-C6H4-C6H4, 4,4′-C6H4CH
CHC6H4, 4,4′-C6H4NNC6H4, 4,4′-C6H4CCC6H4) have been prepared. Electrochemical study has shown that the two metal centers in ...
An Efficient Synthesis of Terminal Allenes from Terminal 1-Alkynes
Jinqiang Kuang and Shengming MaThe Journal of Organic Chemistry2009 74 (4), 1763-1765An Efficient Synthesis of Terminal Allenes from Terminal 1-Alkynes
Jinqiang Kuang and Shengming MaThe Journal of Organic Chemistry2009 74 (4), 1763-1765We have developed a modified method for the synthesis of terminal allenes from terminal 1-alkyne: The reaction of 1-alkynes with 1.8 equiv of Cy2NH and 2.5 equiv of paraformaldehyde mediated by CuI (0.5 equiv) in refluxing dioxane may produce terminal ...
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History
- Published In Issue May 19, 2004
- Received October 22, 2003
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