164401-06-3Relevant articles and documents
Gold-catalyzed tandem annulations of pyridylhomopropargylic alcohols with propargyl alcohols
Li, Xue-Song,Xu, Dan-Tong,Niu, Zhi-Jie,Li, Ming,Shi, Wei-Yu,Wang, Cui-Tian,Wei, Wan-Xu,Liang, Yong-Min
supporting information, p. 832 - 836 (2021/02/16)
A gold-catalyzed tandem annulation of propargylic alcohols and pyridylhomopropargylic alcohols is achieved, providing an atom-economical approach to a diverse set of polycyclic dihydrobenzofurans in good yields. The reaction proceeds via the 5-endo-dig cyclization/Meyer?Schuster rearrangement/Friedel?Crafts-type pathway. In this way, three C?C bonds and one C? O bond form to give a polycyclic skeleton in a one-pot process. Moreover, the products exhibit unique optical properties, which reveal their potential application value.
Lewis-Acid-Catalyzed Tandem Cyclization by Ring Expansion of Tertiary Cycloalkanols with Propargyl Alcohols
Kong, Xiangtao,Li, Xue-Song,Li, Yuke,Liang, Yong-Min,Liu, Hong-Chao,Niu, Zhi-Jie,Wang, Cui-Tian,Wei, Wan-Xu,Zhang, Zhe
supporting information, p. 9457 - 9462 (2021/12/14)
A new method for the efficient synthesis of hexahydro-1H-fluorene and octahydrobenzo[a]azulene derivatives through a ring-expansion strategy is reported. With an appropriate combination of thulium(III) trifluoromethanesulfonate and 13X molecular sieves, a range of unsaturated polycyclic compounds were obtained in good yields. Mechanism studies reveal that the reaction is more likely to undergo Meyer–Schuster rearrangement, ring expansion, and Friedel–Crafts-type pathways, which provide a conceptually different strategy for the ring opening of tertiary cycloalkanols.
Synthesis of 1H-Pyrrolo[1,2-a]indoles via Lewis Acid-Catalyzed Annulation of Propargylic Alcohols with 2-Ethynylanilines
Du, Li-Juan,Han, Ya-Ping,Liang, Yong-Min,Zhang, Hong-Yu,Zhang, Yuecheng,Zhao, Jiquan
supporting information, (2020/03/04)
A novel highly efficient, environmentally benign Lewis acid-catalyzed, and protection-free protocol for the construction of valuable polycyclic products bearing a 1H-pyrrolo[1,2-a]indole scaffold is described, starting from readily available propargylic alcohols and 2-ethynylanilines. The one-pot transformation entails the cleavage of one C?O bond, and the construction of two C?N bonds and one C?C double bond. This unique operationally simple method is performed under mild conditions and in air, producing water as the only byproduct; it is scalable and demonstrates good functional group compatibility and broad scope.
Lewis Acid-Catalyzed Annulation of Propargylic Alcohols with (Z)-2-Styryl-1H-Indoles
Li, Xue-Song,Han, Ya-Ping,Zhu, Xin-Yu,Xia, Yu,Wei, Wan-Xu,Li, Ming,Liang, Yong-Min
supporting information, p. 4441 - 4445 (2018/10/15)
A novel copper(II) trifluoromethanesulfonate-catalyzed intermolecular cascade annulation strategy for the construction of a great variety of pentacyclic compounds possessing valuable carbazole fragments was developed employing propargylic alcohols and (Z)-2-styryl-1H-indoles as the initial substrates. This protocol, which entails a sequential Meyer-Schuster rearrangement/isomerization/-cyclization cascade, enables facile and atom-economical access to various pentacyclic compounds with broad functional-group tolerance in good yields under mild conditions. The conversion could be efficiently scaled up to gram quantities, accentuating a potential application of this work. (Figure presented.).
TMSCl-mediated synthesis of α,β-unsaturated amides via C-C bond cleavage and C-N bond formation of propargyl alcohols with trimethylsilyl azide
Song, Xian-Rong,Song, Bo,Qiu, Yi-Feng,Han, Ya-Ping,Qiu, Zi-Hang,Hao, Xin-Hua,Liu, Xue-Yuan,Liang, Yong-Min
, p. 7616 - 7625 (2014/09/16)
A new method with high efficiency for the synthesis of α,β- unsaturated amides from the easily prepared propargyl alcohols and TMSN 3 using TMSCl as an acid promoter is developed. A wide variety of α,β-unsaturated amides were produced in moderate to excellent yields. Mechanistic studies indicate that this transformation involves TMSCl-mediated allenylazide intermediate formation, C-C bond cleavage, and C-N bond formation. Significantly, this reaction shows good functional group compatibility and high regioselectivity, with a relatively short reaction time and inexpensive reagents.
Lewis acid mediated tandem reaction of propargylic alcohols to tetrazoles involving C-O- and C-C-bond cleavage reactions and a C-N-bond formation
Song, Xian-Rong,Han, Ya-Ping,Qiu, Yi-Feng,Qiu, Zi-Hang,Liu, Xue-Yuan,Xu, Peng-Fei,Liang, Yong-Min
supporting information, p. 12046 - 12050 (2015/03/31)
A novel and direct synthesis of 1-aryl-5-arylvinyl-tetrazoles from easily prepared propargylic alcohols and TMSN3 is developed in the presence of TMSCl under mild conditions (TMS=trimethylsilyl). The process involves an allenylazide intermediate, followed by a C-C-bond cleavage and C-N-bond formation to afford the desired products. Moreover, this method offers a good functional-group applicability and can be scaled-up to grams (yield up to 85%).
State in solution, structure, and regioselectivity of reactions of the lithium 1-(2-methoxyphenyl)-3,3-diphenylpropyne derivative
Dem'yanov,Krut'ko,Borzov,Luk'yanov,Petrosyan
, p. 1939 - 1947 (2007/10/03)
According to the spectrophotometric data, the lithium 1-(2-methoxyphenyl)-3,3-diphenylpropyne derivative in diethyl ether exists as contact ion pairs, while in THF, according to the spectrophotometric and 13C NMR data, solvent-separated ion pairs are predominantly formed. According to the 13C NMR data, the carbanion in the solvent-separated ion pairs has a structure close to the propargylic type. The regioselectivity of reactions of the lithium derivative with ethyl halides in diethyl ether, THF, and hexamethyphosphoramide, with benzyl chloride in the first two solvents, and with methanol in THF were studied. The protonation with methanol proceeds exclusively at the allenylic center (C-1) while the ethylation and especially benzylation proceed predominantly at the propargylic center (C-3). The selectivity of ethylation of the propargylic center of both solvent-separated ion pairs in THF and contact ion pairs in diethyl ether increases as the hardness of the ethylating agent increases, and in the case of the same ethyl halide, the selectivity increases from the solvent-separated ion pairs to the contact ion pairs. The spectral data obtained and the data on changes in the regioselectivity do not allow one to believe that the contact ion pairs of the lithium derivative in ether exhibit the intramolecular coordination of the lithium cation to the methoxy group, which might lead to the allenylic structure of contact ion pairs of this derivative.
