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Intermolecular 1,2-dialkylation reaction method of olefine compound under photoredox/iron (II) catalytic system

A catalytic system and dialkylation technology, applied in the field of intermolecular 1,2-dialkylation reactions of olefinic compounds, can solve limited and other problems

Active Publication Date: 2018-10-12
NANCHANG HANGKONG UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, existing methods are still quite limited and limited to two modes, including alkylarylation and acylation, through the inherent aryl C(Sp 2 )-H cyclization process, and it is realized at a relatively high reaction temperature
As far as the inventors know, using different C(sp 3 )-H bond to achieve an example of intermolecular dialkylation of alkenes has never been reported

Method used

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  • Intermolecular 1,2-dialkylation reaction method of olefine compound under photoredox/iron (II) catalytic system
  • Intermolecular 1,2-dialkylation reaction method of olefine compound under photoredox/iron (II) catalytic system
  • Intermolecular 1,2-dialkylation reaction method of olefine compound under photoredox/iron (II) catalytic system

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Experimental program
Comparison scheme
Effect test

Embodiment 17

[0065]

[0066] The p-methylstyrene of formula I-2 was used as the raw material, and the rest of the reaction raw materials, operations and parameters were the same as in Example 1 to obtain the target product IV-2 with a yield of 70%. dr=1.3:1; light yellow oily liquid; 1 H NMR (400MHz, CDCl 3)δ: 8.09(d, J=7.2Hz, 1.0H), 7.80(d, J=7.6Hz, 1.0H), 7.58(t, J=7.0Hz, 0.50H), 7.50-7.44(m, 1.66H ),7.33(t,J=6.8Hz,1.0H),7.17(d,J=7.6Hz,1.0H), 7.11-7.05(m,2.0H),6.94(d,J=7.6Hz,1H), 4.67-4.58(m,1.0H),4.23-4.15(m,1.0H),3.83-3.73(m,2.0H),2.32-2.20(m,4.0H),1.96-1.93(m,1.0H), 1.70-1.65(m, 1.0H), 1.54-1.43(m, 4.0H), 1.38-1.32(m, 1.0H), 1.26-1.20(m, 2.0H), 1.07-1.05(m, 2.0H), 0.94-0.84(m,4H); 13 C NMR (100MHz, CDCl 3 ( ), 41.5, 34.6, 34.4 (2C), 34.2, 31.7, 31.5, 26.5, 26.5, 26.1, 25.8, 21.1, 20.9, 14.1, 13.6; LRMS (EI, 70eV) m / z (%): 392 (M + ,1), 374(10), 278(28), 105(100); HRMS m / z(ESI) calcd for C 26 h 33 o 3 ([M+H] + ) 393.2424, found 393.2432.

Embodiment 18

[0068]

[0069] The p-bromostyrene of formula I-4 was used as the raw material, and the rest of the reaction raw materials, operations and parameters were the same as in Example 1 to obtain the target product IV-4 with a yield of 75%. dr=1.1:1; light yellow oily liquid; 1 H NMR (400MHz, CDCl 3 )δ: 8.08(d, J=7.6Hz, 2H), 7.61(t, J=7.2Hz, 1H), 7.50(t, J=7.6Hz, 2H), 7.43(d, J=8.0Hz, 2H) ,7.18(d,J=8.0Hz,2H),4.56(d,J=10.4Hz,1H), 3.82-3.76(m,3H),1.95-1.85(m,1H),1.72-1.61(m,2H ),1.54-1.34(m,7H), 1.07-1.02(s,2H),0.91-0.86(m,4H); 13 C NMR (100MHz, CDCl 3 )δ: 193.4, 167.7, 140.4, 136.7, 133.7, 131.4, 130.3, 128.8, 128.7, 120.5, 61.4, 61.3, 42.3, 42.0, 34.5, 34.4, 31.5, 26.4, 26.1, 25.8, 13.7, 70eVI )m / z(%):458(M + +2,1),456 (M + ,1),440(5),342(16),105(100);HRMS m / z(ESI)calcd for C 25 h 30 79 BrO 3 ([M+H] + ) 457.1373, found 457.1381.

Embodiment 19

[0071]

[0072] Using p-cyanostyrene of formula I-5 as raw material, the reaction temperature is 100° C., and the rest of the reaction raw materials, operations and parameters are the same as in Example 1 to obtain the target product IV-5 with a yield of 46%. dr=1.1:1; light yellow oily liquid; 1 H NMR (400MHz, CDCl 3 )δ:8.08(d,J=8.0Hz,1.0H),7.80(d,J=7.6Hz,1.0H), 7.63-7.60(m,1.6H),7.52-7.42(m,3.54H),7.41 -7.32(m,2.0H),4.66(d,J=10.8Hz,0.48H),4.62(d,J=10.8Hz,0.50H),4.22-4.15(m,1H),3.95-3.85(m, 1H), 3.80-3.75(m,1H),1.91-1.88(m,1.0H),1.71-1.34(m,6.0H),1.26-1.20(m,3H), 1.09-1.04(m,2H), 0.88-0.84(m,4H); 13 C NMR (100MHz, CDCl 3 )δ: 193.1, 192.8, 168.0, 167.4, 147.5, 147.3, 136.5, 136.3, 133.8, 133.5, 132.0, 129.4, 129.1, 128.8, 128.6, 128.5, 128.3, 118.7, 1178.7, 110.3.6, 6, ,60.8,42.8,42.51, 41.72,41.1,34.6,34.4,34.3,34.2,31.6,31.4,26.3,26.3,25.9,25.9,25.7,14.0,13.6; (EI,70eV)m / z(%):403 (M + ,1),298(11),192(8),105(100); HRMS m / z(ESI) calcd for C 26 h 30 NO 3 ([M+H] + ...

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Abstract

The invention discloses an intermolecular 1,2-dialkylation reaction method of an olefine compound under a photoredox / iron (II) catalytic system. According to the method, the olefine compound shown inI, a compound as shown in the formula II and a 1,3-dicarbonyl compound as shown in the formula III are subjected to intermolecular 1,2-dialkylation reaction of olefins under the photoredox catalysis / ferrous iron concerted catalytic system to obtain a series of compounds as shown in the formula IV. The method has the advantages that the technology is simple, reaction conditions are mild, the methodis environmentally friendly, the reaction substrates are wide in application range, and the yield is high.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to an intermolecular 1,2-dialkylation reaction method of olefin compounds under a photoredox / iron (II) catalytic system. Background technique [0002] The rapid increase of molecular complexity from readily available chemicals (especially feedstocks derived from the petroleum industry, such as alkenes, alkanes, and aromatics) through mild, economical, and practical selective catalytic pathways is an important area of ​​interest in academia and One of the main goals of the industry. In this field, the functionalization of molecules through the transformation of olefins and / or C–H bonds is an attractive and challenging goal, which has aroused great interest among researchers. Typical strategies include the two-carbon functionalization of alkenes, which extends the carbon chain by introducing two ortho-carbyl functional groups to give structurally complex compoun...

Claims

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Application Information

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IPC IPC(8): C07C67/343C07C69/738C07C253/30C07C255/57C07D317/62C07D319/12
CPCC07C67/343C07C253/30C07D317/62C07D319/12C07C2601/02C07C2601/08C07C2601/14C07C2601/18C07C2603/74C07C69/738C07C255/57
Inventor 宋仁杰雍馨李金恒
Owner NANCHANG HANGKONG UNIVERSITY
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