双官能团硫脲催化剂催化的α-氟代-β-羰基三氟甲基偕二醇的不对称反应研究
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摘要
本文中主要介绍两个方面的工作：合成一系列三氟甲基双羰基化合物,进一步氟化得到α-氟代-β-羰基三氟甲基偕二醇合成砌块。研究三氟甲基双羰基化合物和α-氟代-β-羰基三氟甲基偕二醇合成砌块参与的不对称催化反应,进一步研究了脱三氟乙酸反应机理,发展了一种通过脱三氟乙酸策略构建单氟手性中心的不对称催化合成方法。
第一部分主要介绍了含氟砌块的合成：从三氟乙酸乙酯出发,合成得到三氟甲基1,3-双羰基化合物,进一步利用亲电氟化试剂Selectfluor对双羰基的亚甲基(α-位引入氟原子)进行氟化得到了一系列α-氟代-β-羰基三氟甲基偕二醇合成砌块,利用核磁和单晶衍射对它们的结构进行了表征。
第二部分主要介绍了含氟双羰基化合物和α-氟代-β-羰基三氟甲基偕二醇合成砌块在双官能团硫脲催化剂催化下的不对称反应,以优异的对映选择性构建了单氟手性中心化合物：1)含氟双羰基化合物和α-氟代-β-羰基三氟甲基偕二醇在Takemoto催化剂的催化下,与硝基苯乙烯衍生物发生脱三氟乙酸的不对称催化Micheal加成反应,ee值达到98%的含两个手性中心的单氟化合物,催化反应最高达到91%的高收率、20：1的非对映选择性和98%ee的对映选择性。2)通过α-氟原子和三氟甲基偕二醇对不活泼的酮类底物进行活化,研究了在金鸡纳碱衍生硫脲催化剂催化下通过脱三氟乙酸的策略构筑单氟手性中心的不对称aldol氟化反应,得到了优异光学纯度的含两个手性中心的含氟3-羟基-2-吲哚酮类化合物,催化反应最高达到99%的收率、99：1的非对映选择性和98%ee的优异对映选择性。3)利用选择性断裂碳-碳键的策略,研究了α-氟代-β-羰基三氟甲基偕二醇和磺酰胺底物的不对称Mannich反应,向有机分子结构中引入单氟手性中心,得到了优异光学纯度的含两个手性中心的含氟胺类化合物,最高达到72%的中等产率、5：1的非对映选择性和98%ee的优异对映选择性。从合成方法学角度丰富不对称催化Mannich反应,并对反应机理及相关应用进行研究。
This dissertation focuses mainly on two aspects: synthesis a series of trifluoromethyl β-dicarbonyl compounds, elcctrophilic fluorination of trifluoromethyl β-dicarbonyl compounds to synthesize a series of trilluoromethyl α-fluorinated gem-diol compounds. Mainly studies on the asymmetric reaction of trilluoromethyl P-dicarbonyl and α-fluorinated trifluoromethyl gem-diol compounds. Then extending the fluorinated building blocks and studying the mechanism of releasing trifluoroacetate group.
The first part describes the synthesis of fluorinated building blocks: used the ethyl trilluoroacetate and aryl/alkyl/heteroaryl acetophenons to synthesize a series of trilluoromethyl β-dicarbonyl building blocks, then synthesize series of α-fluorinated trilluoromethyl gem-diol compounds by the available fluorinating reagent Selectlluo under mild reaction conditions.
The second part introduces the asymmetric constructions of chiral fluorinated tertiary center via organocatalytie reactions using trilluoromethyl β-dicarbonyl and α-fluorinated trilluoromelhyl gem-diol compounds:1) In this part has been developed an efficient and highly enantioselective catalytic Michael addition reaction using chiral thiourea tertiary amine derivatives as the catalyst, which stresses on the release of trifluoroacetate as a strategy for cleavage of C-C bond. The resulting decarboxylated y-nitro-α-fluorocarbonyl products with two contiguous centers were obtained in91%yields with good diastereoselcclivities (up to20:1dr) and excellent enantioseleelivics (up to98%ee).2) In this part has been developed a new and efficient direct aldol reaction of gem-diols to isatins catalyzed by cinchona alkaloid hi functional thiourea catalyst. The key step ol' this protocol lies on the release of trilluoroacetate for cleavage of C-C bond by making use of gem-diols as a synthetic equivalent of fluorinaled aryl/alkyl methyl ketone enolates. The resulting deearboxylated chiral lluorinated3-hydroxy-3-phenacyloxindole products were obtained almost quantitatively (up to99%) with excellent diastereoseleetivities (99:1dr) and enantioselectivies (83%-98%ee).3) In this part, the uses the strategy of selective cleavage of carbon-carbon bonds through the mild release of trifluoroacetate group to build lluorinated building blocks and developed a new and efficient direct Mannieh reaction of α-fluorinated trifluoromethyl gem-diol compounds to tert-butyl aryl/alkyl/heteroaryl-(phenylsulfonyl)methylcarbamate catalyzed by cinchona alkaloid bifunctional thiourea catalyst. The resulting decarboxylated fluorinated chiral amino products were obtained almost moderate yield (up to72%), diastereoselectivities (up to5:1dr) and enantioselectivies (up to89%ee).
第一部分主要介绍了含氟砌块的合成：从三氟乙酸乙酯出发,合成得到三氟甲基1,3-双羰基化合物,进一步利用亲电氟化试剂Selectfluor对双羰基的亚甲基(α-位引入氟原子)进行氟化得到了一系列α-氟代-β-羰基三氟甲基偕二醇合成砌块,利用核磁和单晶衍射对它们的结构进行了表征。
第二部分主要介绍了含氟双羰基化合物和α-氟代-β-羰基三氟甲基偕二醇合成砌块在双官能团硫脲催化剂催化下的不对称反应,以优异的对映选择性构建了单氟手性中心化合物：1)含氟双羰基化合物和α-氟代-β-羰基三氟甲基偕二醇在Takemoto催化剂的催化下,与硝基苯乙烯衍生物发生脱三氟乙酸的不对称催化Micheal加成反应,ee值达到98%的含两个手性中心的单氟化合物,催化反应最高达到91%的高收率、20：1的非对映选择性和98%ee的对映选择性。2)通过α-氟原子和三氟甲基偕二醇对不活泼的酮类底物进行活化,研究了在金鸡纳碱衍生硫脲催化剂催化下通过脱三氟乙酸的策略构筑单氟手性中心的不对称aldol氟化反应,得到了优异光学纯度的含两个手性中心的含氟3-羟基-2-吲哚酮类化合物,催化反应最高达到99%的收率、99：1的非对映选择性和98%ee的优异对映选择性。3)利用选择性断裂碳-碳键的策略,研究了α-氟代-β-羰基三氟甲基偕二醇和磺酰胺底物的不对称Mannich反应,向有机分子结构中引入单氟手性中心,得到了优异光学纯度的含两个手性中心的含氟胺类化合物,最高达到72%的中等产率、5：1的非对映选择性和98%ee的优异对映选择性。从合成方法学角度丰富不对称催化Mannich反应,并对反应机理及相关应用进行研究。
This dissertation focuses mainly on two aspects: synthesis a series of trifluoromethyl β-dicarbonyl compounds, elcctrophilic fluorination of trifluoromethyl β-dicarbonyl compounds to synthesize a series of trilluoromethyl α-fluorinated gem-diol compounds. Mainly studies on the asymmetric reaction of trilluoromethyl P-dicarbonyl and α-fluorinated trifluoromethyl gem-diol compounds. Then extending the fluorinated building blocks and studying the mechanism of releasing trifluoroacetate group.
The first part describes the synthesis of fluorinated building blocks: used the ethyl trilluoroacetate and aryl/alkyl/heteroaryl acetophenons to synthesize a series of trilluoromethyl β-dicarbonyl building blocks, then synthesize series of α-fluorinated trilluoromethyl gem-diol compounds by the available fluorinating reagent Selectlluo under mild reaction conditions.
The second part introduces the asymmetric constructions of chiral fluorinated tertiary center via organocatalytie reactions using trilluoromethyl β-dicarbonyl and α-fluorinated trilluoromelhyl gem-diol compounds:1) In this part has been developed an efficient and highly enantioselective catalytic Michael addition reaction using chiral thiourea tertiary amine derivatives as the catalyst, which stresses on the release of trifluoroacetate as a strategy for cleavage of C-C bond. The resulting decarboxylated y-nitro-α-fluorocarbonyl products with two contiguous centers were obtained in91%yields with good diastereoselcclivities (up to20:1dr) and excellent enantioseleelivics (up to98%ee).2) In this part has been developed a new and efficient direct aldol reaction of gem-diols to isatins catalyzed by cinchona alkaloid hi functional thiourea catalyst. The key step ol' this protocol lies on the release of trilluoroacetate for cleavage of C-C bond by making use of gem-diols as a synthetic equivalent of fluorinaled aryl/alkyl methyl ketone enolates. The resulting deearboxylated chiral lluorinated3-hydroxy-3-phenacyloxindole products were obtained almost quantitatively (up to99%) with excellent diastereoseleetivities (99:1dr) and enantioselectivies (83%-98%ee).3) In this part, the uses the strategy of selective cleavage of carbon-carbon bonds through the mild release of trifluoroacetate group to build lluorinated building blocks and developed a new and efficient direct Mannieh reaction of α-fluorinated trifluoromethyl gem-diol compounds to tert-butyl aryl/alkyl/heteroaryl-(phenylsulfonyl)methylcarbamate catalyzed by cinchona alkaloid bifunctional thiourea catalyst. The resulting decarboxylated fluorinated chiral amino products were obtained almost moderate yield (up to72%), diastereoselectivities (up to5:1dr) and enantioselectivies (up to89%ee).
引文
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