115085-23-9Relevant academic research and scientific papers
Bifunctional phosphine ligand-enabled gold-catalyzed direct cycloisomerization of alkynyl ketones to 2,5-disubstituted furans
Hu, Xiaojun,Zhou, Bingwei,Jin, Hongwei,Liu, Yunkui,Zhang, Liming
supporting information, p. 7297 - 7300 (2020/07/14)
An efficient synthesis of 2,5-disubstituted furans directly from alkynyl ketones has been developed via tandem gold(i)-catalyzed isomerization of alkynyl ketones to allenyl ketones and cycloisomerization. The key to the success of this chemistry is the use of a biphenyl-2-ylphosphine ligand featuring a critical remote tertiary amino group.
Gold-Catalyzed Hydroamination of Propargylic Alcohols: Controlling Divergent Catalytic Reaction Pathways to Access 1,3-Amino Alcohols, 3-Hydroxyketones, or 3-Aminoketones
Laserna, Victor,Porter, Michael J.,Sheppard, Tom D.
, p. 11391 - 11406 (2019/09/30)
A versatile approach to the valorization of propargylic alcohols is reported, enabling controlled access to three different products from the same starting materials. First, a general method for the hydroamination of propargylic alcohols with anilines is described using gold catalysis to give 3-hydroxyimines with complete regioselectivity. These 3-hydroxyimines can be reduced to give 1,3-amino alcohols with high syn selectivity. Alternatively, by using a catalytic quantity of aniline, 3-hydroxyketones can be obtained in high yield directly from propargylic alcohols. Further manipulation of the reaction conditions enables the selective formation of 3-aminoketones via a rearrangement/hydroamination pathway. The utility of the new chemistry was exemplified by the one-pot synthesis of a selection of N-arylpyrrolidines and N-arylpiperidines. A mechanism for the hydroamination has been proposed on the basis of experimental studies and density functional theory calculations.
Cascade Reaction of Propargyl Amines with AgSCF3, as Well as One-Pot Reaction of Propargyl Amines, AgSCF3, and Di- tert-butyl Peroxide: Access to Allenyl Thiocyanates and Allenyl Trifluoromethylthioethers
Zhen, Long,Yuan, Kun,Li, Xiu-Yan,Zhang, Chenyun,Yang, Jun,Fan, Hui,Jiang, Liqin
supporting information, p. 3109 - 3113 (2018/05/28)
An efficient cascade reaction of propargyl amines with AgSCF3 and KBr is developed, affording allenyl thiocyanates at room temperature in high yields. This transformation proceeds via the in situ formation of isothiocyanate intermediates, followed by a [3,3]-sigmatropic rearrangement. The resulting allenyl thiocyanates bearing 3-(electro-donating phenyl) substitutions without isolation can then be reacted with di-tert-butyl peroxide and AgSCF3 under reflux to generate novel allenyl trifluoromethylthioether compounds in moderate to good yields via a "one-pot" three-step process.
Gem-Digold Acetylide Complexes for Catalytic Intermolecular [4 + 2] Cycloaddition: Having Two Gold Centers Is Better for Asymmetric Catalysis
Nanko, Masaki,Shibuya, Satoru,Inaba, Yuya,Ono, Soichiro,Ito, Shigekazu,Mikami, Koichi
supporting information, p. 7353 - 7357 (2018/10/15)
Gold(I)-catalyzed highly enantioselective intermolecular [4 + 2] cycloaddition is shown with ynones and cyclohexadiene. Various bicyclo[2.2.2]octadiene derivatives are produced in high yields (up to 99%) with good enantioselectivity (up to 96% ee). Key to the success is generation of the gem-digold terminal alkyne as a catalytic on-cycle species. As proof of the gem-digold catalysis, a positive nonlinear effect is clarified between the ee's of the ligand and the cycloadduct.
Gold-Catalyzed 1,4-Carbooxygenation of 3-En-1-ynamides with Allylic and Propargylic Alcohols via Non-Claisen Pathways
Giri, Sovan Sundar,Lin, Li-Hsuan,Jadhav, Prakash Daulat,Liu, Rai-Shung
supporting information, p. 590 - 596 (2017/02/23)
Gold-catalyzed 1,4-carbooxygenations of 3-en-1-ynamides with allylic alcohols and propargylic alcohols yield α,β-unsaturated amides through non-Claisen pathways; the mechanisms involve ionization of the initial gold enol ethers to form C-bound gold dienolates that capture allylic or propargylic cations to yield the observed products. Our18O-labeling experiments exclude a direct gold-catalyzed allylation or propargylation on these 3-en-1-ynamides. (Figure presented.).
Synthesis of Vinyl-, Allyl-, and 2-Boryl Allylboronates via a Highly Selective Copper-Catalyzed Borylation of Propargylic Alcohols
Mao, Lujia,Bertermann, Rüdiger,Emmert, Katharina,Szabó, Kálmán J.,Marder, Todd B.
supporting information, p. 6586 - 6589 (2017/12/26)
An efficient methodology for the synthesis of vinyl-, allyl-, and (E)-2-boryl allylboronates from propargylic alcohols via Cu-catalyzed borylation under mild conditions is reported. In the presence of commercially available Cu(OAc)2 or Cu(acac)2 and Xantphos, the reaction affords the desired products in up to 92% yield with a broad substrate scope (43 examples). Isolation of an allenyl boronate as the reaction intermediate suggests that an insertion-elimination-type reaction, followed by borylcupration, is involved in the borylation of propargylic alcohols.
Gold(I)-Catalyzed Synthesis of Tetrahydrocarbazoles via Cascade [3,3]-Propargylic Rearrangement/[4+2] Cycloaddition of Vinylindoles and Propargylic Esters
Pirovano, Valentina,Arpini, Elisa,Dell'acqua, Monica,Vicente, Rubén,Abbiati, Giorgio,Rossi, Elisabetta
supporting information, p. 403 - 409 (2016/02/12)
A gold(I)-catalyzed cascade [3,3]-propargylic rearrangement and [4+2] cycloaddition reaction of 2-vinylindoles with propargylic esters is reported. The reaction leads to the synthesis of highly substituted tetrahydrocarbazole derivatives in high yields and diasteroselectivities. Furthermore, a preliminary screening for an asymmetric version of this reaction is described.
Regio- and stereo-selective intermolecular [2+2] cycloaddition of allenol esters with C60 leading to alkylidenecyclobutane-annulated fullerenes
Ueda, Mitsuhiro,Sakaguchi, Tsukasa,Hayama, Miho,Nakagawa, Takafumi,Matsuo, Yutaka,Munechika, Aiko,Yoshida, Shunsuke,Yasuda, Hiroshi,Ryu, Ilhyong
supporting information, p. 13175 - 13178 (2016/11/09)
The intermolecular [2+2] cycloaddition of allenol esters, which were in situ generated by Pt-catalyzed 1,3-acyloxy migration of propargylic esters, with C60 proceeded regio- and stereo-selectively to give a novel class of alkylidenecyclobutane-annulated fullerenes. The cyclobutane-annulated fullerene derivatives have high-lying LUMO levels, which gave a high open-circuit voltage in organic solar cell applications. The observed high electron mobility provided a good fill factor compared with the PCBM-based devices.
HBF4-Catalysed Nucleophilic Substitutions of Propargylic Alcohols
Barreiro, Elena,Sanz-Vidal, Alvaro,Tan, Eric,Lau, Shing-Hing,Sheppard, Tom D.,Dez-Gonzlez, Silvia
supporting information, p. 7544 - 7549 (2016/01/26)
The activity of HBF4 (aqueous solution) as a catalyst in propargylation reactions is presented. Diverse types of nucleophiles were employed in order to form new C-O, C-N and C-C bonds in technical acetone and in air. Good to excellent yields and good chemoselectivities were obtained using low acid loading (typically 1 mol-%) under simple reaction conditions. The activity of HBF4 (aq. solution) as a catalyst in propargylation reactions is presented. C-O, C-N and C-C bonds were formed in technical acetone and in air. Good to excellent yields were obtained using low acid loading (typically 1 mol-%) under mild reaction conditions.
Silver-Catalyzed Cyclization of Propargylic Amides to Oxazolines
Wong, Valerie H. L.,White, Andrew J. P.,Hor,Hii
supporting information, p. 3943 - 3948 (2016/01/25)
A ligand-accelerated effect is observed in the cyclization of propargylic amides catalyzed by bis(pyridyl)silver(I) complexes, with an unexpected reversal of electronic demand to the analogous NH addition reaction. The catalyst was found to be effective for internal alkyne substrates, offering exclusive selectivity for the 5-exo-dig product. Differences in selectivity profile between gold- and silver-catalyzed processes are highlighted and discussed.
