13601-86-0Relevant articles and documents
Selectivity for Alkynyl or Allenyl Imidamides and Imidates in Copper-Catalyzed Reactions of Terminal 1,3-Diynes and Azides
Ghorai, Sourav,Lee, Daesung
supporting information, p. 697 - 701 (2021/02/01)
Copper-catalyzed reactions of terminal 1,3-diynes with electron-deficient azides to generate either 3-alkynyl or 2,3-dienyl imidamides and imidates are described. The selectivity depends on the diyne substituents and the nucleophile that reacts with the ketenimide intermediate generated from the corresponding triazole precursor. Reactions of 1,3-diynes containing a propargylic acetate afford [3]cumulenyl imidamides, while reactions using methanol as the trapping agent selectively generate 2,3-dienyl imidates. Five-membered heterocycles were obtained from 1,3-diynes containing a homopropargylic hydroxyl or amine substituent.
Copper-catalyzed one-pot synthesis of alkynylphophonates
Song, Wang-Ze,Li, Jun-Hao,Li, Ming,He, Jun-Nan,Dong, Kun,Ullah, Karim,Zheng, Yu-Bin
supporting information, p. 697 - 703 (2019/02/16)
Copper is found to be an effective catalyst for the preparation of alkynylphophonates. A novel copper-catalyzed one-pot synthesis of alkynylphophonates from terminal alkynes and dialkyl phosphites is developed which involves the haloalkynes intermediates. This method provides a unique and alternative approach to the well-documented oxidative coupling or arylpropiolic acid strategies.
Highly Selective Syn Addition of 1,3-Diones to Internal Ynamides Catalyzed by Zinc Iodide
Plamont, Rémi,Graux, Lionel V.,Clavier, Hervé
supporting information, p. 1372 - 1376 (2018/04/02)
1,3-Diones are already established as nucleophiles to perform additions to ynamides; the highly selective hydroalkoxylation of internal ynamides is now described. Several catalytic systems have been compared to perform this transformation, including transition-metal-based catalysts and Lewis acids. ZnI2 was found to be both very active and highly selective providing only E adducts through a syn addition. Investigation of the scope and limitations showed that this catalyst was compatible with various functional groups. In addition to seventeen examples of ynamide hydroalkoxylation, one example of ynamide hydroarylation is reported.
Silyl Group-Directed 6-exo-dig Iodocyclization of Homopropargylic Carbamates and Amides
Okitsu, Takashi,Nakahigashi, Hikaru,Sugihara, Ryosuke,Fukuda, Ikki,Tsuji, Saki,In, Yasuko,Wada, Akimori
supporting information, p. 18638 - 18642 (2018/12/04)
Iodocyclization of silyl group-substituted homopropargylic carbamates and amides proceeded via 6-exo-dig mode to afford 6-vinylene-4,5-dihydro-1,3-oxazines in moderate to quantitative yields. This is the first report for silyl group-solely directed iodocy
Copper-Catalyzed Alkynylboration of Alkenes with Diboron Reagents and Bromoalkynes
Gong, Tian-Jun,Yu, Shang-Hai,Li, Kuan,Su, Wei,Lu, Xi,Xiao, Bin,Fu, Yao
supporting information, p. 2884 - 2888 (2017/10/30)
An efficient method for the synthesis of homopropargylboronates by copper-catalyzed alkynylboration of alkenes with diboron reagents and bromoalkynes has been developed. The alkynylboration reaction features high selectivity and efficiency, mild reaction conditions, wide substrate scope, and functional-group compatibility, and is a highly attractive complement to existing methods for the synthesis of homopropargylboronates. Both the boryl and alkynyl groups are good potential functional groups for the subsequent manipulations that provide access to a variety of important molecule structures.
Iridium-Catalyzed Highly Regioselective Azide-Ynamide Cycloaddition to Access 5-Amido Fully Substituted 1,2,3-Triazoles under Mild, Air, Aqueous, and Bioorthogonal Conditions
Song, Wangze,Zheng, Nan
supporting information, p. 6200 - 6203 (2017/11/24)
A highly regioselective method to access 5-amido fully substituted 1,2,3-triazoles by iridium-catalyzed azide-ynamide cycloaddition under mild, air, aqueous, and bioorthogonal conditions is reported. The excellent regioselectivities may derive from the strong coordination between the carbonyl oxygen of ynamide and the -acidic iridium. Since the iridium ion is insensitive to oxygen/water and exhibits low cytotoxicity, it could catalyze this reaction in both organic and biological environments efficiently. Preparation in gram-scale and application in carbohydrates highlight this method.
Copper-catalyzed extended pummerer reactions of ketene dithioacetal monoxides with alkynyl sulfides and ynamides with an accompanying oxygen rearrangement
Murakami, Kei,Imoto, Junichi,Matsubara, Hiroshi,Yoshida, Suguru,Yorimitsu, Hideki,Oshima, Koichiro
supporting information, p. 5625 - 5630 (2013/06/26)
The first examples of metal-catalyzed extended Pummerer reactions through the activation of sulfoxides are described. The copper-catalyzed reactions of ketene dithioacetal monoxides with alkynyl sulfides and ynamides provided a wide variety of γ,γ-disulfanyl-β,γ-unsaturated carbonyl compounds with an accompanying oxygen rearrangement. The products can be easily converted into 1,4-dicarbonyl compounds and substituted heteroaromatics. DFT calculations and mechanistic experiments revealed a new interesting stepwise addition/oxygen rearrangement mechanism. Beyond Pummerer: The first examples of copper-catalyzed extended Pummerer reactions of ketene dithioacetal monoxides with alkynyl sulfides and ynamides provided a wide variety of γ,γ-disulfanyl-β,γ-unsaturated carbonyl compounds with an accompanying oxygen rearrangement (see scheme). The products can be easily converted into 1,4-dicarbonyl compounds and substituted heteroaromatics. DFT calculations and mechanistic experiments revealed a new interesting stepwise addition/oxygen-rearrangement mechanism.
Intramolecular carbocupration of N-aryl-ynamides: A modular indole synthesis
Gati, Wafa,Couty, Francois,Boubaker, Taoufik,Rammah, Mohamed M.,Rammah, Mohamed B.,Evano, Gwilherm
supporting information, p. 3122 - 3125 (2013/07/26)
A modular indole synthesis based on an intramolecular 5-endo-dig carbocupration starting from readily available N-aryl-ynamides is reported. A variety of ynamides are converted to indoles in moderate to good yields and with varying substitution pattern on the indole ring. This further extends the synthetic utility of ynamides in organic synthesis and provides additional insights on the use of intramolecular carbometalation reactions.
Cycloaddition-based formal C-H alkynylation of isoindoles leading to the synthesis of air-stable fluorescent 1,3-dialkynylisoindoles
Ohmura, Toshimichi,Kijima, Akihito,Komori, Yusuke,Suginome, Michinori
supporting information, p. 3510 - 3513 (2013/08/23)
Reaction of N-alkylisoindoles with (bromoethynyl)triisopropylsilane afforded 1,3-bis(triisopropylsilylethynyl) isoindoles in high yields. The formal C-H alkynylation proceeds under transition-metal-free conditions through [4 + 2] cycloaddition of the pyrrole ring of isoindole with bromoalkyne followed by ring-opening of the product.
(Aryloxy)methylsilane Derivatives as New Cholesterol Biosynthesis Inhibitors: Synthesis and Hypocholesterolemic Activity of a New Class of Squalene Epoxidase Inhibitors
Gotteland, Jean-Pierre,Brunel Isabelle,Gendre, Fabrice,Desire, Jerome,Delhon, Andre,at al.
, p. 3207 - 3216 (2007/10/03)
A series of 3-substituted (aryloxy)silane derivatives of benzylamine (4' 4', or 4") was synthesized and evaluated for hypocholesterolemic activity.Most of the new silane derivatives were identified as potent inhibitors of pig liver squalene epoxidase with
