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Method for preparing amine compounds based on novel catalytic Curtius rearrangement reaction

An amine compound, rearrangement reaction technology, applied in the preparation of organic compounds, the preparation of aminohydroxy compounds, steroid compounds, etc., can solve the problem of few C-N bonds, and achieve the effect of efficient synthesis and rapid construction

Active Publication Date: 2020-12-04
NANJING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In the catalytic decarboxylation cross-coupling reaction, it is usually used as a carbon source for the formation of C-C bonds, but rarely used for the formation of C-N bonds

Method used

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  • Method for preparing amine compounds based on novel catalytic Curtius rearrangement reaction
  • Method for preparing amine compounds based on novel catalytic Curtius rearrangement reaction
  • Method for preparing amine compounds based on novel catalytic Curtius rearrangement reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] Preparation of 2,2,2-trichloroethyl-((1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indole-3-)methyl)carbamate ester

[0053] The target product passes through the reaction process and post-processing. Purification by column chromatography afforded 94.0 mg of the target product (93% isolated yield).

[0054] 1 H NMR (400MHz, Chloroform-d) δ7.64(d, J=8.5Hz, 2H), 7.49(d, J=8.4Hz, 2H), 7.03(d, J=2.5Hz, 1H), 6.81(d ,J=9.0Hz,1H),6.66(dd,J=9.1,2.6Hz,1H),5.25(t,J=5.5Hz,1H),4.76(s,2H),4.53(d,J=5.5Hz ,2H),3.81(s,3H),2.42(s,3H); 13 C NMR (101MHz, Chloroform-d) δ168.4, 156.2, 154.7, 139.6, 136.5, 133.7, 131.3, 131.0, 129.9, 129.3, 115.6, 115.1, 112.1, 101.3, 95.7, 74.7, 55.8, 35.4, 13.2; )v 3344, 2929, 1732, 1682, 1591, 1478, 1221, 1045, 811, 721cm -1 ; HRMS (ESI) Calcd.for C21 h 18 Cl 4 N 2 o 4 Na[M+Na] + 524.9913,found 524.9908.

Embodiment 2

[0056] Preparation of 2,2,2-trichloroethyl((R)-3-((3R,7R,8R,9S,10S,13R,14S,17R)-3,7-dihydroxy-10,13-dimethyl Hexadecylhydro-1H-cyclopenta[a]phenanthrene-17-)butyl)carbamate

[0057]

[0058] The target product passes through the reaction process and post-processing. Purification by column chromatography afforded 93.2 mg of the target product (87% isolated yield).

[0059] 1 H NMR (400MHz, Chloroform-d) δ4.95(t, J=6.1Hz, 1H), 4.72(s, 2H), 3.84(q, J=3.0Hz, 1H), 3.49–3.42(m, 1H) ,3.34–3.26(m,1H),3.21–3.12(m,1H),2.19(q,J=12.7Hz,1H),2.00–1.94(m,2H),1.92–1.86(m,1H),1.84 –1.78(m,2H),1.72–1.59(m,4H),1.52–1.45(m,6H),1.41–1.33(m,3H),1.31–1.09(m,7H),0.97(d,J= 6.6Hz,4H),0.90(s,3H),0.65(s,3H); 13 C NMR (101MHz, Chloroform-d) δ154.6, 95.9, 74.6, 72.1, 68.6, 56.1, 50.6, 42.9, 41.6, 40.0, 39.7, 39.5, 39.0, 36.0, 35.4, 35.2, 34.8, 33.9, 32.9, 30.8 ,28.5,23.8,22.9,20.7,18.7,11.9; IR (neat) v3445,3347,2932,2867,2133,1715,1520,1251,1141,731cm -1 ; HRMS (ESI) Calcd.for C 26 h 42 Cl 3 ...

Embodiment 3

[0061] Preparation of 2,2,2-trichloroethyl(4-(N,N-dipropylsulfamoyl)phenyl)carbamate

[0062]

[0063] The target product passes through the reaction process and post-processing. Purification by column chromatography afforded 67.8 mg of the target product (79% isolated yield). 1 H NMR (400MHz, Chloroform-d) δ7.77 (d, J = 8.7Hz, 2H), 7.57 (d, J = 8.7Hz, 2H), 7.29 (brs, 1H), 4.84 (s, 2H), 3.08 –3.04(m,4H),1.59–1.50(m,4H),0.86(t,J=7.4Hz,6H); 13 C NMR (101MHz, Chloroform-d) δ151.4, 140.9, 135.3, 128.6, 118.6, 95.1, 74.8, 50.2, 22.1, 11.3; IR (neat) v3319, 2966, 1751, 1596, 1533, 1207, 1151, 590cm -1 ; HRMS (ESI) Calcd.for C 15 h 22 Cl 3 N 2 o 4 S[M+H] + 431.0361,found 431.0362.

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Abstract

The invention relates to a method for preparing amine compounds based on a novel catalytic Curtius rearrangement reaction. Transition metal catalyzed formation of sp<2> C-N bond is an effective methodfor synthesizing arylamine, a coupling reaction for catalyzing sp<3> C-N bond is also reported, but a method for simultaneously realizing generation of sp<2> C-N bond and sp<3> C-N bond is relativelynot fully developed. According to the method, organic carboxylic acid with rich resources is used as a carbon source, alkyl / aryloxy acyl azide easy to prepare is used as a nitrogen source, under thecatalysis of DMAP and Cu(OAc)2 as low as 0.1mol%, gas N2 and CO2 are used as unique byproducts, and protected alkyl, alkenyl and aryl amine compounds are generated through a one-pot method. The reaction can be applied to later functionalization of natural products and drug molecules, synthesis of chiral alkylamine and rapid construction of different ureas and primary amines. Mechanism research shows that the reaction is carried out through cascade carboxylic acid activation, azidation, Curtius rearrangement and nucleophilic addition reaction.

Description

technical field [0001] The invention relates to the construction of C-N bonds, in particular to a method for generating alkyl, alkenyl and arylamines based on catalytic decarboxylation to construct C-N bonds. Background technique [0002] Nitrogen-containing compounds widely exist in alkaloids, amino acids, functional materials and natural products, and are closely related to life science, material science and human health, so the construction of C-N bonds is very important in organic synthesis. [0003] Since 1990, great progress has been made in the field of transition metal-catalyzed C-N bond coupling, such as copper-catalyzed Ullmann reaction, palladium-catalyzed Buchwald-Hartwig amination reaction and Chan-Lam amination reaction, etc., but these reactions are generally limited to sp 2 Construction of C-N bonds. while sp 3 The construction of C-N bonds mainly relies on traditional methods, such as nitrogen nucleophilic substitution, the Mitsunobu reaction of alcohol...

Claims

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Application Information

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IPC IPC(8): C07D209/14C07C247/00C07J9/00C07C303/40C07C311/47C07C269/00C07C271/20C07J43/00C07D213/81C07C213/02C07C217/58
CPCC07D209/14C07C247/00C07J9/00C07C303/40C07C269/00C07J43/003C07D213/81C07C213/02C07C311/47C07C271/20C07C217/58
Inventor 陆红健葛霞张一品
Owner NANJING UNIV
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