33467-76-4Relevant articles and documents
Cleavage of vinyl carbon-silicon bond in γ-trimethylsilyl allylic alcohols
Al-Hassan,Miller
, p. 3641 - 3645 (2001)
Cleavage of the vinyl carbon-silicon bond by fluoride ion requires a free hydroxyl group located in such a position that stable cyclic transition state can be attained.
PREPARATION OF ALLYL ALCOHOLS FROM MONOHALO- AND GEM-DIHALOBUTYLCYCLOPROPANES IN THE PRESENCE OF COPPER AND ITS SALTS
Korneva, O. S.,Nefedov, O. M.
, p. 2194 - 2196 (1991)
The reaction of gem-dibromo- or gem-dichlorobutylcyclopropanes with an equimolar amount of CuSO4*5H2O in a mixture of DMSO and water is accompanied by scission of the three-membered ring and formation of the corresponding 2-bromo- or 2-chloroallyl alcohols.The corresponding allyl alcohols were prepared analogously from monobromo- or monochlorocyclopropanes.
Copper-Catalyzed Azide–Ynamide Cyclization to Generate α-Imino Copper Carbenes: Divergent and Enantioselective Access to Polycyclic N-Heterocycles
Chen, Yang-Bo,Deng, Chao,Liu, Rai-Shung,Liu, Xin,Luo, Chen,Wang, Ze-Shu,Ye, Long-Wu,Zhai, Tong-Yi,Zhang, Yi-Ping
supporting information, p. 17984 - 17990 (2020/08/21)
Here an efficient copper-catalyzed cascade cyclization of azide-ynamides via α-imino copper carbene intermediates is reported, representing the first generation of α-imino copper carbenes from alkynes. This protocol enables the practical and divergent synthesis of an array of polycyclic N-heterocycles in generally good to excellent yields with broad substrate scope and excellent diastereoselectivities. Moreover, an asymmetric azide–ynamide cyclization has been achieved with high enantioselectivities (up to 98:2 e.r.) by employing BOX-Cu complexes as chiral catalysts. Thus, this protocol constitutes the first example of an asymmetric azide–alkyne cyclization. The proposed mechanistic rationale for this cascade cyclization is further supported by theoretical calculations.
Synthesis of (5Z,7E)-dodecane-5,7-diene-1-alcohol as well as acetate and propionate thereof
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Paragraph 0029-0031, (2019/03/28)
The invention belongs to the technical field of insect pheromone synthesis, and discloses a new method for synthesizing (5Z,7E)-dodecane-5,7-diene-1-alcohol as well as acetate and propionate thereof.The method takes propynol as an initial raw material to be subjected to coupling with 1-bromobutane to generate 2-heptyne-1-alcohol, triple bond is reduced to be E-type double bond through LiAlH4, 2-heptyne-1-alcohol is oxidized to be olefine aldehyde through PDC, olefine aldehyde reacts with a Wittig reagent (5-ethyoxyl-5-oxopentyl)triphenyl phosphonium bromide to produce (5Z,7E)-dodecane-5,7-dienoic acid ethyl ester which is reduced by LiAlH4 to obtain (5Z,7E)-dodecane-5,7-diene-1-alcohol, (5Z,7E)-dodecane-5,7-diene-1-alcohol reacts with acetyl chloride and propionyl chloride finally to obtain (5Z,7E)-dodecane-5,7-diene-1-alcohol acetate and (5Z,7E)-dodecane-5,7-diene-1-alcohol propionate. The method utilizes LiAlH4 to reduce the triple bond to be the E-type double bond, and utilizes theWittig reaction of the Wittig reagent with the tail end provided with ester group and aldehyde to directly build the Z-type double bond, the synthesis route is simple, convenient and efficient, and the reaction condition is moderate and environmentally friendly.
Rhodium-Catalyzed Synthesis of α,β-Unsaturated Ketones through Sequential C-C Coupling and Redox Isomerization
Li, Hong-Shuang,Guo, Guili,Zhang, Rui-Ze,Li, Fei
supporting information, p. 5040 - 5043 (2018/08/24)
A novel Rh(I)-catalyzed sequential C-C coupling and redox isomerization between allylic alcohols and 1,3-dienes has been accomplished. This versatile protocol provides expeditious access to a broad range of polysubstituted α,β-unsaturated ketones with excellent atom economy and regioselectivity.
Synthesis and pyrolysis of two flavor precursors of oct-1-en-3-yl methylpyrazinecarboxylates
Lai, Miao,Ji, Xiaoming,Tao, Tao,Shan, Yuanyuan,Liu, Pengfei,Zhao, Mingqin
, p. 1627 - 1638 (2017/05/19)
To rich flavor additive species of pyrazines, two new compounds of 3,6-dimethyl-2,5-pyrazinedicarboxylic acid 1-octen-3-yl ester (DMPOE) and 3,5,6-trimethyl-2-pyrazinecarboxylic acid 1-octen-3-yl ester (TMPOE) were synthesized by KMnO4 oxidatio
Electronic interactions between a stable electride and a nano-alloy control the chemoselective reduction reaction
Ye, Tian-Nan,Li, Jiang,Kitano, Masaaki,Sasase, Masato,Hosono, Hideo
, p. 5969 - 5975 (2016/08/31)
Controlling the electronic structure of heterogeneous metal catalysts is considered an efficient method to optimize catalytic activity. Here, we introduce a new electronic effect induced by the synergy of a stable electride and bimetallic nanoparticles for a chemoselective reduction reaction. The electride [Ca24Al28O64]4+·(e-)4, with extremely low work function, promotes the superior activity and selectivity of a Ru-Fe nano-alloy for the conversion of α,β-unsaturated aldehydes to unsaturated alcohols in a solvent-free system. The catalyst is easily separable from the product solution and reusable without notable deactivation. Mechanistic studies demonstrate that electron injection from the electride to the Ru-Fe bimetallic nanoparticles promotes H2 dissociation on the highly charged active metal and preferential adsorption of CO bonds over CCs bond of the unsaturated aldehydes, to obtain the thermodynamically unfavorable but industrially important product.
Visible-Light Promoted Distereodivergent Intramolecular Oxyamidation of Alkenes
Ren, Xiang,Guo, Qihang,Chen, Jianhui,Xie, Hujun,Xu, Qing,Lu, Zhan
supporting information, p. 18695 - 18699 (2016/12/26)
The visible-light-promoted diastereodivergent intramolecular oxyamination of alkenes is described to construct oxazolindinones, pyrrolidinones and imidazolidones via mild generation of primary amidyl radicals from functionalized hydroxylamines. A unique phenomenon of highly diastereoselective ring-opening of aziridines controlled by electron sacrifices was observed. Highly diastereoselective amino alcohols derivatives were obtained efficiently through this protocol in gram scales. The mechanistic studies suggested the isolatable anti-aziridine intermediates were generated quickly from primary amidyl radicals and the diastereoselectivities were controlled by pKavalues of the electron sacrifices.
Highly enantioselective copper(i)-catalyzed conjugate addition of 1,3-diynes to α,β-unsaturated trifluoromethyl ketones
Sanz-Marco, Amparo,Blay, Gonzalo,Mu?oz, M. Carmen,Pedro, José R.
supporting information, p. 8958 - 8961 (2015/05/27)
The conjugate diynylation of α,β-unsaturated trifluoromethyl ketones is carried out in the presence of a low catalytic load (2.5 mol%) of a copper(i)-MeOBIPHEP complex, triethylamine and a terminal 1,3-diyne. Pre-metalation of the terminal 1,3-diyne with stoichiometric or higher amounts of dialkylzinc reagent is not required. The corresponding internal diynes bearing a propargylic stereogenic center are obtained with good yields and excellent enantioselectivities. This journal is
Preparation and odour properties of (S)-3-mercapto-1-heptyl acetate
Liang, Sen,Sun, Baoguo,Yang, Shaoxiang,Liu, Yongguo,Tian, Hongyu,Liu, Yuping,Chen, Haitao
, p. 343 - 346 (2014/07/08)
Synthesis of (S )-3-mercapto-1-heptyl acetate was achieved in four steps. Sharpless asymmetric epoxidation of (E )-2-heptenol yielded (2R,3R )-2,3-epoxy-1-heptanol, which was treated with thiourea in the presence of Ti(OPri)4 to give (2S,3S )-2,3-epithio- 1-heptanol, reduction of which followed by acetylation afforded (S )-3-mercapto-1-heptyl acetate in 91% ee. The optically active product possessed a tropical fruit aroma reminiscent of mango and passion fruit, with berry, ester-like, sweet, and pepper-like aspects.
