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Method for synthesizing axially chiral allene compound under catalysis of trivalent rhodium

A compound and axial chirality technology, which is applied in the field of trivalent rhodium catalyzed synthesis of axial chiral allene compounds, can solve the problems of uncommon and limited biaryl compounds, and achieves easy preparation, good enantioselectivity and reaction conditions. mild effect

Active Publication Date: 2021-07-23
SHAANXI NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] There are many strategies for the construction of chiral molecules through the activation of trirhodium-catalyzed asymmetric C-H bonds, such as alkenylation, desymmetry, and cyclization; however, reports on the synthesis of chiral molecules by kinetic resolution are not common
On the other hand, the synthesis of axial chiral molecules through chiral rhodium catalysis is still limited to the synthesis of biaryls, and the asymmetric synthesis of axial chiral allenes is still a great challenge.

Method used

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  • Method for synthesizing axially chiral allene compound under catalysis of trivalent rhodium
  • Method for synthesizing axially chiral allene compound under catalysis of trivalent rhodium
  • Method for synthesizing axially chiral allene compound under catalysis of trivalent rhodium

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Synthesis of 2-(1,2-dien-1-yl)-N-methoxybenzamide skeleton compound with the following structural formula

[0031]

[0032] Under air atmosphere, add 16.6mg (0.11mmol) N-methoxybenzamide, 52.9mg (0.2mmol) 4,4-dimethyl-1,3-diphenylpenta-1 -Alkyn-3-ol, 4.6mg (0.004mmol) [Cp X Rh(III)], 41.7mg (0.05mmol) chiral zinc carboxylate Zn1, 3mL 1,2-dichloroethane, tighten the pressure tube, stir and react at room temperature for 24 hours to make N-methoxybenzamide basically react completely , after the reaction was completed, 1,2-dichloroethane was removed by rotary evaporation under reduced pressure to obtain a crude product, which was passed through a column with silica gel (petroleum ether:ethyl acetate=10:1~3:1) to obtain a white solid Product, its yield is 54% (yield is calculated based on propargyl alcohol), and characterization data is: 1 H NMR (600MHz, CDCl 3 )δ8.34(s,1H),7.86(d,J=9.1Hz,1H),7.53(t,J=7.4Hz,1H),7.46(t,J=7.5Hz,1H),7.38–7.34( m,3H),7.32–7.28(m,5H),7.23–...

Embodiment 2

[0034] Synthesis of 2-(1,2-dien-1-yl)-N-methoxybenzamide skeleton compound with the following structural formula

[0035]

[0036] In this example, the N-methoxybenzamide used in Example 1 was replaced with equimolar 4-methyl-N-methoxybenzamide, and the other steps were the same as in Example 1 to obtain a white solid, Its yield is 38%, and characterization data is:1 H NMR (600MHz, CDCl 3 )δ8.29(s,1H),7.72(d,J=7.9Hz,1H),7.31–7.29(m,2H),7.25–7.24(m,2H),7.23–7.20(m,4H),7.16 –7.15(m,2H),7.14–7.13(d,J=7.3Hz,2H),7.11(s,1H),2.96(s,3H),2.36(s,3H),1.22(s,9H); 13 C NMR (151MHz, CDCl 3 )δ201.3, 165.7, 142.0, 136.5, 136.4, 134.5, 131.7, 130.4, 129.6, 129.3, 129.1, 129., 128.4, 127.6, 127.4, 126.2, 120.4, 108.3, 63.5, 36.1, 29.8, 2 Theoretical value C 28 h 29 NNaO 2 + [M+Na] + : 434.2091, measured value: 434.2085; HPLC: chiral column AD-H (n-hexane:isopropanol=95:5, 1.0mL / min, 40 ℃, 254nm); tr(major)=9.0min, tr(minor )=7.0min, 90%ee.

Embodiment 3

[0038] Synthesis of 2-(1,2-dien-1-yl)-N-methoxybenzamide skeleton compound with the following structural formula

[0039]

[0040] In this embodiment, the N-methoxybenzamide used in Example 1 is replaced with equimolar 4-phenyl-N-methoxybenzamide, and other steps are the same as in Example 1 (the reaction time is 30h ), obtain white solid product, and its yield is 50%, and characteristic data is: 1 H NMR (600MHz, CDCl 3 )δ8.5(s,1H),7.97(d,J=8.1Hz,1H),7.72(dd,J=8.1,1.8Hz,1H),7.66–7.61(m,3H),7.49–7.47(m ,2H),7.43–7.37(m,2H),7.36–7.30(m,6H),7.29–7.27(m,2H),7.21(t,J=7.2Hz,1H),3.06(s,3H), 1.30(s,9H); 13 C NMR (151MHz, CDCl 3 )δ201.5,165.4,144.3,139.7,136.4,136.3,135.2,131.1,130.9,129.7,129.3,129.1,129.0,128.4,128.3,127.6,127.5,127.2,126.9,126.3,120.6,108.3,63.6,36.1,29.8 ; HRMS (ESI) calculated for C 33 h 31 NNaO 2 + [M+Na] + :496.2247, found: 496.2244; HPLC: chiral column AD-H (n-hexane:isopropanol=95:5, 1.0mL / min, 40°C, 254nm); tr(major)=9.9min, tr(minor) =7.9min, 9...

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Abstract

The invention discloses a method for synthesizing an axially chiral allene compound under the catalysis of trivalent rhodium, which comprises the following steps: taking [CpXRh (III)] which is easy to prepare, high in catalytic activity and controllable in site selection as a catalyst, taking an N-methoxybenzamide compound and a propargyl alcohol compound as raw materials, and promoting by chiral carboxylic acid zinc salt to obtain a tetra-substituted axially chiral allene compound. The method is simple to operate, the raw materials are stable and easy to prepare, the reaction conditions are mild, and the substrate application range is wide. In the prior art, axially chiral allene is synthesized under the catalysis of trivalent rhodium, an optically pure propargyl alcohol substrate is mostly required to be used, and a target product is converted through a chiral transfer strategy; according to the method, the defects are overcome, the synthesis of the axial chiral allene compound can be realized by taking racemic propargyl alcohol as a raw material, the yield is extremely high, and the enantioselectivity is good (as high as 95%).

Description

technical field [0001] The invention relates to a method for synthesizing an axial chiral allene compound catalyzed by trivalent rhodium. Background technique [0002] Allene compounds widely exist in natural products, drug molecules, and material molecules. So far, people have found allene structures in more than 150 natural products and drugs. Due to their unique skeleton structure, allene compounds can also be used as important organic synthesis intermediates to participate in organic transformations (such as carbon metallation, nuclear metallation, electrophilic addition, nucleophilic addition and free radical addition) ( Acc. Chem. Res. 2019, 52, 1301). Therefore, chemists have made great efforts to develop facile synthetic methods for allenes, especially optically pure allene compounds. [0003] Transition metal-catalyzed C–H bond activation, as an efficient and concise synthetic method, has achieved rapid development in the past decade. The trivalent rhodium cataly...

Claims

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Application Information

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IPC IPC(8): C07C259/10C07D209/48B01J31/22B01J31/04
CPCC07C259/10C07D209/48B01J31/2295B01J31/04C07B2200/07B01J2531/822B01J2531/0225B01J2531/0261B01J2231/4205Y02P20/584
Inventor 李兴伟王芬毛茹霞祝晓晗
Owner SHAANXI NORMAL UNIV
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