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Synthesis and preparation method of bicyclo [3, 3, 0] cyclooctanone derivative

A synthetic method, the technology of cyclooctanone, applied in the field of organic compound synthesis, can solve the problems of complex catalytic system, tedious synthesis of raw materials, limited substrates, etc., and achieve the effect of good universality, good yield and environmental friendliness

Active Publication Date: 2020-08-11
EAST CHINA NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

For example, literature (4) Snider, B.B.; Zhou.J, Org. Lett. 2006, 8, 1283-1286. (5) Mato, R.; Manzano, R.; Reyes, E.; Carrillo, L.; Uria , U.; Vicario, J.L.J.Am.Chem.Soc.2019, 141, 9495-9499. However, this ring shrinkage strategy is still in the development stage. Limited and other disadvantages

Method used

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  • Synthesis and preparation method of bicyclo [3, 3, 0] cyclooctanone derivative
  • Synthesis and preparation method of bicyclo [3, 3, 0] cyclooctanone derivative
  • Synthesis and preparation method of bicyclo [3, 3, 0] cyclooctanone derivative

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Embodiment 1: the synthesis of IA

[0040]

[0041] Eight-membered cycloenone, acid, catalyst, and solvent are respectively selected from (1E,3Z)-ethyl-3-(1-benzyl-1H-indole-3-carbonyl)-4-hydroxy-2-phenylcyclooctyl Alkane-1,3-diene carboxylate, alkene hydrochloric acid, CuCl, dimethyl sulfoxide (DMSO), the amount of raw materials is eight-membered cycloenol (1E,3Z)-ethyl-3-(1-benzyl Base-1H-indole-3-carbonyl)-4-hydroxy-2-phenylcyclooctane-1,3-dienecarboxylate 0.20mmol, dilute hydrochloric acid 0.8mmol, CuCl 0.04mmol, solvent 5mL, in 100 After reacting at ℃ for 6 hours, the target product formula (IA) was obtained as a white solid with an isolated yield of 84%. mp 164-166°C.

[0042] NMR data:

[0043] 1 H NMR (500MHz, Chloroform-d) δ8.49(d, J=8.0Hz, 1H), 7.54(s, 1H), 7.42-7.40(m, 2H), 7.31-7.15(m, 9H), 6.83( d, J=7.3Hz, 2H), 5.14(q, J=15.7Hz, 2H), 4.21(q, J=7.1Hz, 2H), 3.10(dd, J=9.5, 3.1Hz, 1H), 2.59- 2.53(m,1H),2.06-1.94(m,2H),1.87-1.81(m,2H),1.58-1.48(m,1H),...

Embodiment 2

[0045] Embodiment 2: the synthesis of IB

[0046]

[0047]Eight-membered cycloenone, acid, catalyst, and solvent are respectively selected from (1E,3Z)-ethyl-4-hydroxy-2-phenyl-3-(1-p-methylbenzenesulfonyl-1H-pyrrole-3-carbonyl ) cyclooctane-1,3-diene carboxylate, ethylene hydrochloric acid, CuCl, dimethyl sulfoxide (DMSO), the amount of raw materials is respectively eight-membered cycloenol (1E,3Z)-ethyl-4-hydroxyl -2-Phenyl-3-(1-p-methylbenzenesulfonyl-1H-pyrrole-3-carbonyl)cyclooctane-1,3-dienecarboxylate 0.20mmol, dilute hydrochloric acid 0.8mmol, CuCl 0.04mmol , solvent 5mL, and reacted at 100° C. for 6 hours to obtain the target product formula (IB), a yellow solid, and the separation yield was 50%. mp 162-164°C.

[0048] NMR data:

[0049] 1 H NMR (400MHz, Chloroform-d) δ8.02 (d, J=8.3Hz, 2H), 7.72-7.71 (m, 1H), 7.37-7.09 (m, 6H), 6.86-6.85 (m, 1H), 6.12(t,J=3.4Hz,1H),4.32-4.19(m,2H),3.05-3.02(m,1H),2.62-2.54(m,1H),2.45(s,3H),2.31(s, 3H),1.88-1.78(m,2H),1.68-1....

Embodiment 3

[0051] Embodiment 3: the synthesis of IC

[0052]

[0053] Eight-membered cycloalkene, acid, catalyst, and solvent are respectively selected from (1E,3Z)-ethyl-3-(furan-3-carbonyl)-4-hydroxy-2-phenylcyclooctane-1,3-diene Formic acid ester, ene hydrochloric acid, CuCl, dimethyl sulfoxide (DMSO), the amount of raw materials is eight-membered cycloenol (1E,3Z)-ethyl-4-hydroxy-2-phenyl-3-(1- p-Toluenesulfonyl-1H-pyrrole-3-carbonyl) cyclooctane-1,3-dienecarboxylate 0.20mmol, dilute hydrochloric acid 0.8mmol, CuCl 0.04mmol, solvent 5mL, react at 100°C for 6 hours, The target product (IC) was obtained as a yellow oil with an isolated yield of 77%.

[0054] NMR data:

[0055] 1 H NMR (500MHz, Chloroform-d) δ7.54(s, 1H), 7.38-7.28(m, 5H), 7.06(d, J=3.5Hz, 1H), 6.40(dd, J=3.5, 1.5Hz, 1H), 4.33-4.21(m, 2H), 3.14(dd, J=9.4, 3.1Hz, 1H), 2.65-2.59(m, 1H), 2.06-1.83(m, 4H), 1.61-1.52(m, 1H), 1.22(t, J=7.1Hz, 3H). 13 C NMR (126MHz, CDCl 3 )δ204.61, 180.03, 173.55, 171.49, 151.93, 14...

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Abstract

The invention discloses a bicyclo [3, 3, 0] cyclooctanone derivative as shown in a formula (I) (See the specification) and a synthesis method thereof. The bicyclo [3, 3, 0] cyclooctanone derivative asshown in the formula (I) is synthesized from an octatomic cycloenol compound as a raw material under the action of a catalyst and an additive. The preparation method disclosed by the invention has the advantages of simple and easy-to-synthesize raw materials, simple and convenient post-treatment, good universality, good yield, environmental friendliness and the like. The bicyclo [3, 3, 0] cyclooctanone derivative disclosed by the invention is a main structural unit in many natural products and drug molecules, and most of the bicyclo [3, 3, 0] cyclooctanone derivatives have relatively high biological activity and have important research value in the aspect of drug synthesis.

Description

technical field [0001] The invention belongs to the technical field of organic compound synthesis, and relates to a method for synthesizing bicyclo [3,3,0] cyclooctanone derivatives through copper-catalyzed ring shrinkage reaction. Background technique [0002] Five-membered carbocyclic compounds widely exist in various organic compounds. Especially bicyclo[3,3,0]cyclooctane compounds are key skeletons of many drugs and natural products. Based on these, there have been many explorations on the synthesis methods of bicyclo[3,3,0]cyclooctane compounds. Traditional methods for synthesizing bicyclo[3,3,0]cyclooctane compounds usually include intramolecular or intermolecular cyclization reactions and cycloaddition reactions. For example: Literature (1) Millham, A.B.; Kier, M.J.; Leon, R.M.; Karmakar, R.; Stempel, Z.D.; Y.Chem.Comm.2014,50,948-950.(3)Long,R.; Yang,Z.Tetrahedron.2019,75,1746-1750. [0003] Besides, cross-ring reaction, as a third feasible strategy, has also att...

Claims

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Application Information

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IPC IPC(8): C07D209/12C07D207/48C07D307/46C07D333/22C07C67/333C07C69/757
CPCC07D209/12C07D207/48C07D307/46C07D333/22C07C67/333C07C69/757
Inventor 李艳忠穆远洋徐穆榕袁洋王野
Owner EAST CHINA NORMAL UNIV
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