- Access to Natural Valparanes and Daucanes: Enantioselective Synthesis of (-)-Valpara-2,15-diene and (+)-Isodaucene
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The first total synthesis of a natural diterpene valparane, (-)-valpara-2,15-diene (1), has been achieved from all-trans-geranylgeraniol (9), a natural renewable compound. The key steps involve a Ti(III)-mediated radical cyclization of the chiral monoepoxypolyene (14R,15R)-14,15-epoxy,16-tert-butyldimethylsilyloxygeranyllinalyl acetate (8) to give the 6,6,7-tricyclic intermediate 7 with stereocontrolled formation of six stereocenters; a stereo- and regio-directed contraction of the A ring in 7 to produce a cyclopentane ring; and the ready generation of the target isopropenyl group. This research provides access to structurally related natural products such as the sesquiterpene (+)-isodaucene (3), the synthesis of which is also reported herein.
- Quílez Del Moral, José F.,Pérez, álvaro,Herrador, María Del Mar,Barrero, Alejandro F.
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- Synthesis method of teprenone and intermediate thereof
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The invention relates to synthesis methods of teprenone and an intermediate thereof. The synthesis of the intermediate all-trans (5E,9E)-farnesyl acetone comprises: 1) in the presence of a catalyst, carrying out a carroll rearrangement reaction on the mixture of 5E-nerolidol and 5Z-nerolidol and hydrocarbonyl acetoacetate to obtain the isomer mixture of (5Z,9Z)-farnesyl acetone, (5Z,9E)-farnesyl acetone, (5E,9Z)-farnesyl acetone, and (5E,9E)-farnesyl acetone, wherein the content of (5E,9E)-farnesyl acetone in the isomer mixture is controlled at more than 18%; and 2) carrying out low-temperature crystallization separation on the isomer mixture in a moderately polar solvent to obtain the all-trans (5E,9E)-farnesyl acetone. According to the present invention, the high-purity all-trans (5E,9E)-farnesyl acetone is obtained by using the mixture of 5E-nerolidol and 5Z-nerolidol as the raw material through the low-temperature crystallization separation, such that the teprenone with the qualified quality can be conveniently obtained.
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Paragraph 0078; 0079
(2021/08/19)
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- Synthesis method and method for synthesizing plant alcohol, isoplant alcohol and geranyl geraniol by using intermediate farnesylacetone (by machine translation)
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The invention relates to a synthesis method of intermediate farnesyl acetone and a method for synthesizing vitamin E, vitamin K1, vitamin K2 side chain isovegetable alcohol, plant alcohol and geranyl geraniol by using farnesyl acetone, and concretely relates to hydrogenation of 5 - farnesyl -2 - acetone and farnesyl acetone through three Grignard reaction to obtain plant ketone. The farnesyl acetone reacts with the vinyl chloride Grignard reagent to obtain geranyl linalool, the aromatic leaf-based geraniol is rearranged under acid catalysis, or farnesyl acetone is directly reacted with the hydroxyl-protected 2 - chloroethanol Grignard reagent to obtain geraniol. The plant alcohol is reacted with the vinyl chloride Grignard reagent to obtain the plant alcohol, and the plant alcohol is directly reacted with the hydroxyl-protected 2 - chloroethanol Grignard reagent to obtain the plant alcohol. The method has the advantages of cheap and easily available starting materials, short synthetic process steps, low product cost and the like. (by machine translation)
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Paragraph 0061; 0088-0089
(2020/07/21)
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- Process for synthesizing teprenone
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The invention discloses a process for synthesizing teprenone.According to the process for synthesizing teprenone, nerolidol is adopted as an initial raw material and subjected to selenium dioxide and tert-butyl hydroperoxide oxidizing in sequence, nerolidol and dihydropyran are subjected to acid catalysis to form acetal, acetal reacts with a Grignard reagent on the presence of copper salt and reacts with methyl acetoacetate on the presence of aluminum salt, and the teprenone product consistent with the configuration of products sold on the market is obtained through four steps of reactions.According to a preparation method of teprenone, the raw material is cheap and easy to obtain, operation is easy and convenient, the reaction conditions are mild, and industrial production is expected to be achieved.
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- Ozonolysis of alkenes and study of reactions of polyfunctional compounds. LIX. New approach to synthesis of isophytol and (E,E)-geranyllinalool, isoprenoid synthons for the α-tocopherol and (E,E)-α-tocotrienol
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A new approach was developed to the synthesis of racemic isophytol and (E,E)-geranyllinalool starting from a product of partial ozonolysis of (E,E,E)-l,5,9-cyclododecatriene.
- Odinokov,Akhmetova,Savchenko,Mallyabaeva,Lobanova
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p. 1099 - 1101
(2007/10/03)
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- Alkylation du linalol sur les carbones C8 (et C6)
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Metallation of linalool α to the distal double bond with strong bases is described.The corresponding carbanions have been alkylated or oxidized to give mixtures of products resulting from attack at both carbon 8 (major product) and carbon 6 (minor product).
- Cuvigny, Therese,Julia, Marc,Rolando, Christian
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- Inclusion complex compound, process for its production, and method for its use
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An inclusion complex compound comprising (a) meta-cyclophane and (b) a trans-terpenoid of the formula STR1 wherein n is an integer of 1 to 9; A1 and A2 each represent (1) a hydrogen atom, (2) a halogen atom, (3) an inorganic group containing an oxygen, nitrogen or sulfur atom, (4) an organic group containing 1 to 5 carbon atoms, or (5) an organic group containing an oxygen, nitrogen or sulfur atom and 1 to 5 carbon atoms; and C* is the carbon atom of a carbonyl or methylene group, Included by the meta-cyclophane. This inclusion complex compound can be prepared by contacting the meta-cyclophane with a mixture containing the trans-terpenoid. A trans-terpenoid can be separated from a mixture containing it by utilizing an inclusion complex compound of it with meta-cyclophane.
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