1595-64-8Relevant academic research and scientific papers
Rh(III)-Catalyzed [3 + 2] Spirocyclization of 2 H-Imidazoles with 1,3-Diynes for the Synthesis of Spiro-[imidazole-indene] Derivatives
Luo, Yi,Liu, Hao,Zhang, Jing,Liu, Man,Dong, Lin
, p. 7604 - 7608 (2020)
An effective strategy to synthesize spirocyclic compounds, [imidazole-4,1′-indene], has been efficaciously developed relied on Rh(III)-catalyzed [3 + 2] spirocyclization of 2H-imidazoles and 1,3-diynes with excellent chemselectivity and regioselectivity.
Gold-Catalyzed Oxidative Cyclization Involving Nucleophilic Attack to the Keto Group of α,α′-Dioxo Gold Carbene and 1,2-Alkynyl Migration: Synthesis of Furan-3-carboxylates
Wang, Ali,Lu, Mingduo,Liu, Yuanhong
supporting information, p. 6813 - 6818 (2021/09/13)
A multicomponent strategy for the synthesis of functionalized furan-3-carboxylates based on gold-catalyzed oxidative cyclization of diynones with alcohols or water has been developed. Mechanistic studies revealed that a rare nucleophilic attack to the carbonyl group of the α,α′-dioxo gold carbene instead of the carbene center and 1,2-alkynyl group migration were involved in this transformation. This method offers several advantages such as mild conditions, high regio- and chemoselectivity, and wide functional group compatibility.
Copper Catalysis for Selective Heterocoupling of Terminal Alkynes
Su, Lebin,Dong, Jianyu,Liu, Long,Sun, Mengli,Qiu, Renhua,Zhou, Yongbo,Yin, Shuang-Feng
supporting information, p. 12348 - 12351 (2016/10/07)
A Cu-catalyzed selective aerobic heterocoupling of terminal alkynes is disclosed, which enables the synthesis of a broad range of unsymmetrical 1,3-diynes in good to excellent yields. The results disprove the long-held belief that homocouplings are exclusively favored in the Glaser-Hay reaction.
From highly enantioselective catalytic reaction of 1,3-diynes with aldehydes to facile asymmetric synthesis of polycyclic compounds
Turlington, Mark,Du, Yuhao,Ostrum, Samuel G.,Santosh, Vishaka,Wren, Kathryne,Lin, Tony,Sabat, Michal,Pu, Lin
, p. 11780 - 11794 (2011/09/16)
(S)-1,1′-Binaphth-2-ol (BINOL) in combination with ZnEt2, Ti(OiPr)4, and biscyclohexylamine was found to catalyze the highly enantioselective (83-95% ee) addition of various 1,3-diynes to aldehydes of diverse structures. This method provides a convenient pathway to generate a number of optically active dienediynes as the acyclic precursors to polycyclic compounds. The chiral dienediynes undergo highly chemoselective Pauson-Khand (PK) cycloaddition in benzaldehyde by using [Rh(cod)Cl]2 as the catalyst in the presence of rac-BINAP. High diastereoselectivity (up to >20:1) has also been achieved with the chiral dienediyne substrates containing a bulky substituent adjacent to the chiral center. In the presence of the Grubbs II catalyst, ring-closing enyne metathesis of the PK cycloaddition products led to the formation of the desired 5,5,7- and 5,5,8-fused tricyclic compounds. Further highly diastereoselective Diels-Alder reaction of a 5,5,7-tricyclic compound with maleic anhydride produced a 5,5,7,6-polycyclic product. The asymmetric synthesis of polycyclic compounds from optically active dienediynes has established a novel and efficient synthetic route to the structural framework of many biologically significant molecules.
Synthesis of simple diynals, diynones, their hydrazones, and diazo compounds: Precursors to a family of dialkynyl carbenes (R1-C-C- C-C-C-R2)
Bowling, Nathan P.,Burrmann, Nicola J.,Halter, Robert J.,Hodges, Jonathan A.,McMahon, Robert J.
supporting information; experimental part, p. 6382 - 6390 (2010/12/19)
A variety of substituted pentadiynols, -diynals, and -diynones have been prepared en route to precursors to dialkynyl carbenes (R1-C-C-C- C-C-R2). In light of the marginal stability associated with these simple systems, several strategies were required to assemble the carbon backbones. The requisite five-carbon skeletons were prepared using 4 + 1, 3 + 2, 2 + 2 + 1, and 2 + 1 + 1 + 1 coupling methodologies. The Dess-Martin periodinane serves as an excellent method for the oxidation of pentadiynols to diynals and diynones, although many of the oxidized products are sufficiently reactive that they were not isolated; rather, they were generated in situ and intercepted with nucleophiles such as tosylhydrazide or trisylhydrazide. The hydrazone derivatives are generally reliable precursors to diazo compounds and carbenes, although cyclization of the hydrazone to afford a pyrazole can be a complicating factor in certain instances.
Stereoselective synthesis of enynones via base-catalyzed isomerization of 1,5-disubstituted-2,4-pentadiynyl silyl ethers or their alcohol derivatives
Chen, Jingjin,Fan, Guoqin,Liu, Yuanhong
supporting information; experimental part, p. 4806 - 4810 (2010/12/19)
1,5-Disubstituted-2,4-pentadiynyl silyl ethers undergo smooth desilylative isomerization to afford cis-enynones as major products with moderate stereoselectivities in the presence of a catalytic amount of KOtBu or DBU. While the isomerization reactions of their alcohol derivatives catalyzed by KOH, KOtBu or NaH take place efficiently to produce trans-enynones with high stereoselectivities. These reactions provide convenient and practical routes for the synthesis of enynones with a wide range of substitution groups.
One-pot formation and derivatization of di- and triynes based on the Fritsch-Buttenberg-Wiechell rearrangement
Luu, Thanh,Morisaki, Yasuhiro,Cunningham, Nina,Tykwinski, Rik R.
, p. 9622 - 9629 (2008/03/15)
(Chemical Equation Presented) A divergent, one-pot synthesis of functionalized polyynes has been developed. Beginning with the appropriately substituted dibromoolefinic precursor, a carbenoid Fritsch-Buttenberg-Wiechell (FBW) rearrangement is used to gene
A one-pot synthesis and functionalization of polyynes
Morisaki, Yasuhiro,Luu, Thanh,Tykwinski, Rik R.
, p. 689 - 692 (2007/10/03)
A one-pot synthesis and derivatization of diynes and triynes is reported. The polyyne framework is formed from a dibromoolefin precursor based on a carbenoid rearrangement, and the resulting Li-acetylide is then trapped in situ with an electrophile to pro
A Stereoselective Route to 1-Chloro-1-halo-Enynes, Versatile Precursors for the Synthesis of Chloroenediynes and Enetriynes
Alami, Mouad,Crousse, Benoit,Linstrumelle, Gerard
, p. 3687 - 3690 (2007/10/02)
1-Chloro-1-halo-enynes, readily available by metallation of (E)-chloroenynes, undergo sequential coupling with terminal alkynes under Pd-catalysis to produce stereoselectively chloroenediynes and enetriynes in good yields.Keywords: Palladium, chloroenyne, 1-chloro-1haloenyne, α-substituted chloroenyne, chloroenediyne, enetriyne
