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A kind of synthetic method of gem-1,3-enynes

A synthesis method and compound technology, applied in the synthesis field of synthesis methods, can solve the problems of unsatisfactory dimerization selectivity, unsatisfactory selectivity, limited application, etc., and achieve high stereo and position selectivity, catalyst and ligand. Simple, simple effect of catalytic system

Active Publication Date: 2022-03-25
HUNAN FIRST NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, it is a great challenge to effectively control the regio, stereo, and chemoselectivity, especially for the cross-dimerization reaction of two different terminal alkynes (there may be 12 kinds of dimerization products), which limits its further application.
In the 1980s and 1990s, Professor Trost in the United States used Pd(OAc) 2 / TDMPP catalytic system realizes the symmetrical dimerization of terminal alkynes and the cross-dimerization of terminal alkynes and intermediate alkynes, but the system is limited to the cross-gem dimerization of aromatic terminal alkynes and aliphatic terminal alkynes to asymmetric gem-1 , 3-enynes not applicable
Prof. Nakamura and Oshovsky achieved the cross gem-dimerization of aromatic-terminated alkynes and aliphatic-terminated alkynes respectively using complex Ti catalysts, but the use of pre-prepared complex and expensive Ti catalysts limits the further application of this method
Second, expensive Rh catalysts and complex Fe complexes can also catalyze the cross-gem dimerization of aromatic-terminated alkynes and aliphatic-terminated alkynes, but the selectivity is not satisfactory, including self-symmetric dimerization of alkynes and other dimerization of alkynes. Polymerization
Although Sabourin et al. reported a case of complex bimetallic Pd(OAc) 2 / CuI / DIPP / Et 3 The N-catalyzed system realizes the cross-dimerization of phenylacetylene and 2-methyl-3-butyn-2-ol into gem-1,3-enyne compounds, but the participation of metal copper leads to the occurrence of acetylenyne coupling by-products formation, and the dimerization selectivity of the reaction is not ideal
Secondly, in 2019, Yuanzhi Xia and Sunwoo Lee’s team used complex bimetallic Ni / Cu / tetramethylethylenediamine (TMEDA) system to catalyze the decarboxylation of aromatic alkynoic acid and acetylenic alcohol to synthesize gem-1,3-enyne compounds, but also At the same time, a conjugated diyne compound coupling by-product is produced, and in addition, the raw material alkyne acid of this method needs to be pre-prepared

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  • A kind of synthetic method of gem-1,3-enynes
  • A kind of synthetic method of gem-1,3-enynes
  • A kind of synthetic method of gem-1,3-enynes

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preparation example Construction

[0021] A method for synthesizing gem-1,3-enyne compounds, wherein the raw materials for preparing the gem-1,3-enyne compounds include: palladium catalyst, tetramethylethylenediamine, acetylenic alcohol derivatives and aromatic alkynes Hydrocarbons.

[0022]In one embodiment, the palladium catalyst is selected from at least one of palladium chloride, palladium acetate or palladium bromide.

[0023] The structural formula of the asymmetric gem-1,3-enyne compound is as follows shown.

[0024] In one embodiment, in the structural formula I, R 1 , R 2 Independently selected from one of methyl, ethyl, isobutyl, n-nonyl, and phenyl; Ar is selected from phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-trifluoro Methylphenyl, 4-fluorophenyl, 3-chlorophenyl, 4-bromophenyl, 4-cyanophenyl, 4-trifluoromethoxyphenyl, 4-nitrophenyl, 4-methylphenyl Sulfonylphenyl, 4-trimethylsilylphenyl, 4-formylphenyl, 4-dimethylaminophenyl, 4-aminophenyl, 3-hydroxyphenyl, 1-naphthyl, 2-anthracene One of ba...

Synthetic example 1

[0038] Synthesis of 2-methyl-3-methylene-5-phenylpent-4-yn-2-ol

[0039] Add 0.01 mmol of palladium chloride, 0.1 mmol of TMEDA, 0.4 mmol of 2-methyl-3-butyn-2-ol, 0.2 mmol of phenylacetylene, and 0.5 mL of chloroform into the reactor. Under a nitrogen atmosphere, heat to 50°C, keep stirring for 16h, stop the reaction, cool to room temperature, wash with saturated NaCl, then extract with ethyl acetate, dry, evaporate and concentrate under reduced pressure to remove the solvent, and the crude product is separated by column chromatography to obtain Target product, yield 74%. 1 H NMR (400MHz, CDCl 3 ):δ7.46–7.44(m,2H),7.33–7.31(m,3H),5.65(d,J=1.2Hz,1H),5.50(d,J=1.2Hz,1H),1.87(br, 1H), 1.50(s, 6H). 13 CNMR (101MHz, CDCl 3 ): δ139.5, 131.4, 128.2, 128.2, 122.9, 118.3, 91.2, 87.7, 72.7, 29.1.

Synthetic example 2

[0041] Synthesis of 2-methyl-3-methylene-5-(4-(trifluoromethoxy)phenyl)pent-4-yn-2-ol

[0042] Add 0.01 mmol of palladium chloride, 0.1 mmol of TMEDA, 0.4 mmol of 2-methyl-3-butyn-2-ol, 0.2 mmol of 4-trifluoromethoxyphenylacetylene, and 0.5 mL of chloroform into the reactor. Under nitrogen atmosphere, heat to 50°C, continue to stir for 13h, stop the reaction, cool to room temperature, wash with saturated NaCl, then extract with ethyl acetate, dry, evaporate and concentrate under reduced pressure to remove the solvent, and the crude product is separated by column chromatography to obtain Target product, yield 74%. 1 H NMR (400MHz, CDCl 3 ):δ7.48–7.44(m,2H),7.17–7.15(m,2H),5.67(d,J=1.2Hz,1H),5.50(d,J=1.2Hz,1H),1.87(br, 1H), 1.49(s, 6H). 13 C NMR (101MHz, CDCl 3 ): δ148.9(q, J=1.8Hz), 139.2, 133.0, 121.8, 120.8, 120.3(d, J=257.8Hz), 119.0, 89.8, 88.6, 72.7, 29.1.

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Abstract

The invention provides a palladium / tetramethylethylenediamine catalyzed cross-dimerization method of acetylenic alcohol derivatives and aromatic alkyne compounds to form gem-1,3-enyne compounds. The catalyst and the ligand of the method are simple, cheap, and easy to obtain, and have the characteristics of high stereo, regio, and chemoselectivity, good functional group compatibility, easy separation of the obtained target product, simple reaction operation, safety and reliability, and the like. This method mainly solves the problem that other methods require complex and expensive ligands and metal catalysts, and solves the problem that two different alkynes are not easy to cross-dimerize with high selectivity, which has important scientific significance and synthetic application value.

Description

【Technical field】 [0001] The invention relates to the field of organic synthesis, in particular to a synthesis method of gem-1,3-enyne compounds. 【Background technique】 [0002] The conjugated 1.3-enyne is an important structure in organic chemistry, and its derivatives exist in many biologically active natural products. For example, terbinafine is a successful drug molecule for the treatment of superficial fungal infections, while oxamflatin was shown to be a novel antineoplastic compound that inhibits mammalian histone deacetylases. On the other hand, 1,3-enyne is also a useful component in synthetic chemistry, and it can synthesize highly substituted aromatic compounds and other complex functional molecules through various transformations. [0003] Current methods for the preparation of conjugated 1,3-enynes include Wittig or Horner-Wadsworth-Emmons (HWE) reactions of alkyne-containing compounds, transition metal-catalyzed cross-couplings of alkenes and alkynes, and dehy...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C29/32C07C33/30C07C41/30C07C43/23C07C201/12C07C205/19C07C315/04C07C317/22C07C213/02C07C215/68C07C33/48C07C33/28C07C33/34C07D213/30C07F7/08C07F17/02
CPCC07C29/32C07C41/30C07C201/12C07C315/04C07F7/081C07F7/083C07C213/02C07D213/30C07F17/02C07C2601/08C07C2601/14C07C33/30C07C43/23C07C205/19C07C317/22C07C215/68C07C33/483C07C33/28C07C33/34
Inventor 董建玉刘立鑫周永波
Owner HUNAN FIRST NORMAL UNIV