Method for synthesizing 1,3-disubstitute-4-penten-1-one

A compound and disubstituted technology, applied in the field of allyl β-ketoester decarboxylation allyl alkylation reaction, can solve the problems of unstable enol silyl ether and limited application, and achieve mild reaction conditions and easy operation , the effect of high regional selectivity

Inactive Publication Date: 2007-12-12
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2005, Graening and Hartwig reported that iridium complexes catalyzed enol silyl ethers and allyl alcohol carbonates in CsF and ZnF 2 Preparation of 1,3-disubstituted-4-ene-1-pentanones under the condition of additives [Hartwig, J.F.; Craening, T.J.Am.Chem.Soc.2005, 127, 17192-17193.], but due to the use Unstable enol silyl ethers and the need for additives limit the application of this reaction

Method used

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  • Method for synthesizing 1,3-disubstitute-4-penten-1-one

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Embodiment 1: Under the catalysis of iridium complex, the research on the temperature and solvent of the allyl alkylation reaction of decarboxylation:

[0023]

[0024] Wherein, mol means mole, and base means base.

[0025] serial number

[0026] 8

[0027] Among them, THF is tetrahydrofuran, Et 2O is diethyl ether, DME is dimethylethylene ether, Toluene is toluene, DCM is dichloromethane, DBU is 1,8-diazabicyclo[5,4,0]undec-7-ene, DBN is 1,5-diazabicyclo[4,3,0]non-5-ene, and BSA is N,O-bis(trimethylsilyl)acetamide.

Embodiment 2

[0028] Example 2: Research on the allyl alkylation reaction of decarboxylation of different ligands under the catalysis of iridium complexes:

[0029]

[0030] 1a R 3 , R 4 =Ph 1dR 3 , R 4 =Ph

[0031] 1bR 3 , R 4 = 2-Naphthyl

[0032] 1c 3 , R 4 =2-MeO-Ph

[0033] Where Ph is phenyl, Naphthyl is naphthyl and MeO is methoxy.

[0034] serial number

Ligand

time (h)

Yield (%)[b]

3a / 4a

ee(%)

1

1a

16

83

99∶1

95

2

1b

36

21

99∶1

93

3

1c

24

65

＞99∶1

96

4

1d

36

45

94∶6

70

[0035] Example 2: Allyl β-ketoester decarboxylated allyl alkylation reaction under the catalysis of iridium complex

[0036]

[0037] Add [Ir(COD)Cl] sequentially to a dry reaction tube 2 (0.004mmol), chiral ligand (0.008mmol), n-propylamine (0.5mL) and THF (0.5mL),...

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Abstract

The invention provides a method for synthesizing 1, 3- disubstituted - ene- 1- pentanone. It takes iridium complex compound as catalyst and pi-allyl beta- keto acid ester as raw material to synthesize said product with large area and high enantiotropic selection. The invention is characterized by easy got raw material, high- performance catalyst, temperate reacting condition, wide suitable range for substrate, large product area and high enantiotropic selection.

Description

technical field [0001] The present invention relates to a decarboxylation allyl alkylation reaction of allyl β-ketoesters catalyzed by metal complexes, which can achieve high efficiency and high regio- and enantioselective synthesis of 1,3- Disubstituted-4-ene-1-pentanones. Background technique [0002] Transition metal-catalyzed asymmetric allylic alkylation is one of the most important reactions for carbon-carbon bond formation and plays an important role in organic synthesis [(a) Trost, B.M.D.; Van Vranken, L.Chem.Rev .1996, 96, 395-422; (b) Trost, B.M.Acc.Chem.Res.2002, 35, 695-705; (c) Trost, B.M.; Crawley, M.L.Chem.Rev.2003, 103, 2921-2944 .]. In recent years, studies have found that allyl substitution reactions catalyzed by transition metals such as iridium, molybdenum, tungsten, and rhodium have their own characteristics. For example, branched chain products can be generated with high regioselectivity for allyl substrates containing terminal olefins. Many progress...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C49/223C07C45/67B01J31/24B01J31/28
Inventor 游书力贺虎
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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