130708-22-4Relevant academic research and scientific papers
A Method for the Late-Stage Formation of Ketones, Acyloins, and Aldols from Alkenylstannanes: Application to the Total Synthesis of Paecilonic Acid A
Sommer, Heiko,Hamilton, James Y.,Fürstner, Alois
, p. 6161 - 6165 (2017)
Treatment of alkenylstannanes with Cu(OAc)2/Et3N affords the corresponding enol esters or ketones under conditions that proved compatible with many common functionalities; these include groups that would neither survive under the sta
Molybdenum-catalyzed diastereoselective anti-dihydroxylation of secondary allylic alcohols
Su, Shixia,Wang, Chuan
supporting information, p. 2436 - 2440 (2019/03/29)
In this protocol, we report a Mo-catalyzed anti-dihydroxylation of secondary allylic alcohols, providing a general method for the preparation of 1,2,3-triols bearing up to three continuous stereocenters with excellent diastereocontrol. The mechanistic studies reveal that this dihydroxylation reaction consists of two steps and up to excellent diastereomeric ratios of the final triol products can be achieved due to the high level of both diastereocontrol in the initial epoxidation and regiocontrol in the following hydrolysis in situ.
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.
Alkynylation of aldehydes mediated by zinc and allyl bromide: a practical synthesis of propargylic alcohols
Zhou, Ji-Cai,Zhao, Lei,Li, Yuan,Fu, Ding-Qiang,Li, Zi-Cheng,Huang, Wen-Cai
, p. 4283 - 4294 (2017/06/20)
Abstract: A practical synthesis of propargylic alcohols was developed by alkynylation of aldehydes mediated by zinc and allyl bromide. Aromatic, aliphatic and vinyl aldehydes react with phenylacetylene or 1-hexyne to obtain various propargylic alcohols at room temperature in up to 98% yield. This method is characterized with inexpensive materials, wide substrate scope, and mild reaction conditions, and is also easy to scale up. In addition, this protocol is applicable to the alkynylation of α-ketone esters and epoxides to generate α-tertiary-hydroxy esters and α-alkynyl alcohols, respectively. Graphical Abstract: [Figure not available: see fulltext.].
C-F bond cleavage enabled redox-neutral [4+1] annulation via C-H bond activation
Wang, Cheng-Qiang,Ye, Lu,Feng, Chao,Loh, Teck-Peng
supporting information, p. 1762 - 1765 (2017/02/15)
Using α,α-difluoromethylene alkyne as a nontraditional one-carbon reaction partner, a synthetically novel method for the construction of isoindolin-1-one derivatives via Rh(III)-catalyzed [4+1] annulation reaction is reported. The 2-fold C-F bond cleavage not only enables the generation of desired product under an overall oxidant-free condition but also results in a net migration of carbon-carbon triple bond. In addition, the present reaction protocol exhibits a tolerance of a wide spectrum of functional groups due to the mild reaction conditions employed.
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.
Electrocatalytic generation of amidyl radicals for olefin hydroamidation: Use of solvent effects to enable anilide oxidation
Zhu, Lin,Xiong, Peng,Mao, Zhong-Yi,Wang, Yong-Heng,Yan, Xiaomei,Lu, Xin,Xu, Hai-Chao
supporting information, p. 2226 - 2229 (2016/02/19)
Oxidative generation of synthetically important amidyl radicals from N-H amides is an appealing and yet challenging task. Previous methods require a stoichiometric amount of a strong oxidant and/or a costly noble-metal catalyst. We report herein the first electrocatalytic method that employs ferrocene (Fc), a cheap organometallic reagent, as the redox catalyst to produce amidyl radicals from N-aryl amides. Based on this radical-generating method, an efficient intramolecular olefin hydroamidation reaction has been developed. Easy access to N-arylamidyl radicals: The first electrocatalytic method for the generation of amidyl radicals from anilides has been developed using ferrocene (Cp2Fe) as a highly reactive, yet chemoselective redox catalyst. Based on this radical-generating method, a highly chemo- and diastereoselective olefin hydroamidation reaction has been developed.
Iron-catalyzed unexpected easy access to stereodefined trimethylsilyl vinyl ketenes
Chai, Guobi,Fu, Chunling,Ma, Shengming
supporting information; experimental part, p. 4058 - 4061 (2012/10/08)
Stereodefined trimethylsilyl vinyl ketenes with polysubstitution have been synthesized highly regio- and stereoselectively via an iron-catalyzed reaction of 2-trimethylsilyl-2,3-allenoates with Grignard reagents in good to excellent yields. The reaction w
Tetrabutylammonium fluoride (TBAF)-catalyzed addition of substituted trialkylsilylalkynes to aldehydes, ketones, and trifluoromethyl ketones
Chintareddy, Venkat Reddy,Wadhwa, Kuldeep,Verkade, John G.
supporting information; experimental part, p. 4482 - 4488 (2011/07/30)
Herein we report that tetrabutylammonium fluoride (TBAF) is a very efficient catalyst for the addition of trialkylsilylalkynes to aldehydes, ketones, and trifluoromethyl ketones in THF solvent at room temperature. The reaction conditions are mild and oper
Domino gold-catalyzed rearrangement and fluorination of propargyl acetates
De Haro, Teresa,Nevado, Cristina
supporting information; experimental part, p. 248 - 249 (2011/02/23)
A combination of IPrAuNTf2 as catalyst in the presence of Selectfluor has been successfully used for the high yielding synthesis of α-fluoroenones via 1,3-acyloxy rearrangement of propargyl acetates followed by Csp2-F bond formation,
