轴手性膦-噁唑啉配体应用于银（Ⅰ）催化的不对称vinylogous Mannich反应以及叔胺（膦）催化的一些活化烯烃反应研究
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摘要
不对称催化是不对称有机合成中非常重要的一个方面,在近几十年来它已经成为了一个相当活跃的研究领域。本论文的工作主要围绕：(1)轴手性膦-噁唑啉配体应用于金属银(Ⅰ)催化的不对称Mannich反应研究；(2)发展新的叔胺和叔膦催化的活化烯烃的反应,且这部分工作主要侧重于不对称催化方面的研究。本论文分为三个部分：
第一部分：轴手性膦-噁唑啉配体应用于金属银(Ⅰ)催化的不对称Mannich反应研究。(1)从(S)-binol合成的轴手性膦-噁唑啉类配体I-I-L7成功地应用于银(Ⅰ)催化的氟代亚胺与三甲基硅氧基呋喃的不对称Mannich反应中,改反应以高达99%的产率,大于20：1的dr值以及最高81%的ee值得到相应加成产物。(2)基于第(1)部分的工作,我们在氟代亚胺上引入了一个手性辅基[(S)-1-苯乙基],研究了它们与三甲基硅氧基呋喃的不对称Mannich反应。采用10 mo1%的醋酸银和11 mo1%轴手性膦-嗯唑啉类配体I-II-L1配位催化该反应,能以高达99%的产率,大于20：1的dr值以及最高99%的ee值得到相应的氟化γ-丁烯羟酸内酯类衍生物。(3)从(R)-binol合成的轴手性膦-噁唑啉类配体I-III-L6成功地应用于银(Ⅰ)催化的N-Boc亚胺与三甲基硅氧基呋喃的不对称Mannich反应中,该反应能以高达97%的产率、7：1的dr值以及最高86%的ee值得到相应的主要加成产物。由于Boc保护基在一些酸性条件(如三氟乙酸和稀盐酸)下很容易脱去,因此这类反应的合成应用价值得到了进一步的延伸。
第二部分：手性叔胺或叔膦催化缺电子联烯与活化烯烃(C=C)的反应。(1)发展了D-苏氨酸-L-叔亮氨酸衍生的双官能团膦催化的高对映选择性的马来酰亚胺与缺电子联烯的不对称[3+2]的成环反应,以良好到高的收率和ee值合成了具有两个叔碳手性中心的官能团化二并环戊烯类化合物。本节还进一步提出了该反应可能的反应机理以及考察了反应产物的转化。(2)首次考察了手性叔胺β-6’-羟基异辛可宁(β-ICD)催化的高对映选择性的马来酰亚胺与缺电子联烯以及联烯酮的不对称RC反应,以良好到高的收率以及良好到优秀的ee值合成了具有光学活性的高官能团化的联烯类衍生物。在过渡金属催化下,这些产物能够进一步以良好的收率转化合成手性的γ-羟基丁烯羟酸内酯以及呋喃衍生物。
第三部分：叔胺催化缺电子联烯与活化羰基酮(C=O)的反应。(1)首次发展了β-6’-羟基异辛可宁(p-ICD)催化三氟甲基酮与联烯酸酯的不对称[2+2]环加成反应,该反应能够以中等到良好的收率以及良好到较高的非对映选择性和对映选择性,得到S构型的2-烯机取代的氧杂环丁烷类化合物。(2)考察了4-二甲氨基吡啶(DMAP)催化靛红与联烯酸酯的Morita-Baylis-Hillman反应,该反应能以良好到较高的收率以及中等的非对映选择性得到相应的加成产物。这是第一例缺电子联烯与活化羰基酮的Morita-Baylis-Hillman反应。
Asymmetric catalysis is an important aspect of asymmetric synthesis, and one that has seen tremendous activity over the past decades. This dissertation mainly focuses on:(1) axially chiral phosphine-oxazoline ligands in the silver(I)-catalyzed asymmetric Mannich reaction; (2) the discovery of some tertiary amine-or phosphine-catalyzed reactions of activated alkenes especially for their asymmetric versions. This dissertation contains three parts:
Part I:Axially chiral phosphine-oxazoline ligands in the silver(I)-catalyzed asymmetric Mannich reaction. (1) Axially chiral phosphine-oxazoline ligand I-I-L7, prepared from (S)-binol, was found to be a fairly effective chiral ligand in silver(I)-catalyzed asymmetric Mannich reaction of fluorinated aldimines with trimethylsiloxyfuran to give the corresponding adducts in up to 99%yield, over 20:1 dr and 81%ee. (2) Based on the work of (1), a highly regio-and enantioselective asymmetric vinylogous Mannich reaction of readily available fluorinated aldimines bearing a chiral auxiliary [(S)-1-phenylethyl group] with siloxyfurans to afford chiral fluorine-containing y-butenolide derivatives in up to 99%yield along with over 20:1 dr and 99%ee has been developed in the presence of silver acetate (10 mol%) and axially chiral phosphine-oxazoline ligand I-I-L1 (11 mol%). (3) Axially chiral phosphine-oxazoline ligand I-I-L6 derived from (R)-binol was identified as a fairly effective chiral ligand in silver(I)-catalyzed asymmetric Mannich reaction of N-Boc aldimines with trimethylsiloxyfuran, giving the corresponding adducts in up to 97%yield,7:1 dr and 86%ee (major diastereoisomer). Since the N-protecting group (N-Boc) can be readily cleaved under several convenient acidic conditions(HCl or TFA), this reaction will be useful in organic synthesis.
Part II:Chiral tertiary amine-or phosphine-catalyzed reactions of electron-deficient allenes with activated alkenes (C=C). (1) D-Threonine-L-tert-leucine-based bifunctional phosphine-catalyzed highly enantioselective [3+2] annulation of allenes with maleimides has been disclosed, affording the corresponding functionalized bicyclic cyclopentenes containing two tertiary stereogenic centers in good to high yields and with good to high enantioselectivities. The plausible reaction mechanism and the further transformation of cycloadducts have been also disclosed. (2) The first example ofβ-ICD catalyzed highly enantioselective intermolecular Rauhut-Currier reaction of maleimides with allenoates and penta-3,4-dien-2-one has been also disclosed, allowing the synthesis of optically active functionalized allene derivatives in good to high yields along with good to excellent enantioselectivities. These chiral functionalized allenic derivatives can be further transformed to the corresponding chiral y-butenolide derivatives and furan derivatives in good yields in the presence of transition metal catalysts.
Part III:Tertiary amine-catalyzed reactions of electron-deficient allenes with activated ketones (C=O). (1) We have developed the first asymmetric organocatalytic formal [2+2] cycloaddition of trifluoromethylketones and allenoates using (3-isocupreidine (β-ICD) as a catalyst to afford S-configured 2-alkyleneoxetanes in moderate to good yields along with good to high diastereoselectivities and enantioselectivities. (2) We have disclosed a 4-(N,N-dimethylamino)pyridine (DMAP)-catalyzed Morita-Baylis-Hillman reaction of isatins with allenoates, affording the corresponding adducts in good to high yields with moderate diastereoselectivities. This is the first example on the Morita-Baylis-Hillman reaction of the carbonyl group in activated ketone with electron-deficient allenic ester.
第一部分：轴手性膦-噁唑啉配体应用于金属银(Ⅰ)催化的不对称Mannich反应研究。(1)从(S)-binol合成的轴手性膦-噁唑啉类配体I-I-L7成功地应用于银(Ⅰ)催化的氟代亚胺与三甲基硅氧基呋喃的不对称Mannich反应中,改反应以高达99%的产率,大于20：1的dr值以及最高81%的ee值得到相应加成产物。(2)基于第(1)部分的工作,我们在氟代亚胺上引入了一个手性辅基[(S)-1-苯乙基],研究了它们与三甲基硅氧基呋喃的不对称Mannich反应。采用10 mo1%的醋酸银和11 mo1%轴手性膦-嗯唑啉类配体I-II-L1配位催化该反应,能以高达99%的产率,大于20：1的dr值以及最高99%的ee值得到相应的氟化γ-丁烯羟酸内酯类衍生物。(3)从(R)-binol合成的轴手性膦-噁唑啉类配体I-III-L6成功地应用于银(Ⅰ)催化的N-Boc亚胺与三甲基硅氧基呋喃的不对称Mannich反应中,该反应能以高达97%的产率、7：1的dr值以及最高86%的ee值得到相应的主要加成产物。由于Boc保护基在一些酸性条件(如三氟乙酸和稀盐酸)下很容易脱去,因此这类反应的合成应用价值得到了进一步的延伸。
第二部分：手性叔胺或叔膦催化缺电子联烯与活化烯烃(C=C)的反应。(1)发展了D-苏氨酸-L-叔亮氨酸衍生的双官能团膦催化的高对映选择性的马来酰亚胺与缺电子联烯的不对称[3+2]的成环反应,以良好到高的收率和ee值合成了具有两个叔碳手性中心的官能团化二并环戊烯类化合物。本节还进一步提出了该反应可能的反应机理以及考察了反应产物的转化。(2)首次考察了手性叔胺β-6’-羟基异辛可宁(β-ICD)催化的高对映选择性的马来酰亚胺与缺电子联烯以及联烯酮的不对称RC反应,以良好到高的收率以及良好到优秀的ee值合成了具有光学活性的高官能团化的联烯类衍生物。在过渡金属催化下,这些产物能够进一步以良好的收率转化合成手性的γ-羟基丁烯羟酸内酯以及呋喃衍生物。
第三部分：叔胺催化缺电子联烯与活化羰基酮(C=O)的反应。(1)首次发展了β-6’-羟基异辛可宁(p-ICD)催化三氟甲基酮与联烯酸酯的不对称[2+2]环加成反应,该反应能够以中等到良好的收率以及良好到较高的非对映选择性和对映选择性,得到S构型的2-烯机取代的氧杂环丁烷类化合物。(2)考察了4-二甲氨基吡啶(DMAP)催化靛红与联烯酸酯的Morita-Baylis-Hillman反应,该反应能以良好到较高的收率以及中等的非对映选择性得到相应的加成产物。这是第一例缺电子联烯与活化羰基酮的Morita-Baylis-Hillman反应。
Asymmetric catalysis is an important aspect of asymmetric synthesis, and one that has seen tremendous activity over the past decades. This dissertation mainly focuses on:(1) axially chiral phosphine-oxazoline ligands in the silver(I)-catalyzed asymmetric Mannich reaction; (2) the discovery of some tertiary amine-or phosphine-catalyzed reactions of activated alkenes especially for their asymmetric versions. This dissertation contains three parts:
Part I:Axially chiral phosphine-oxazoline ligands in the silver(I)-catalyzed asymmetric Mannich reaction. (1) Axially chiral phosphine-oxazoline ligand I-I-L7, prepared from (S)-binol, was found to be a fairly effective chiral ligand in silver(I)-catalyzed asymmetric Mannich reaction of fluorinated aldimines with trimethylsiloxyfuran to give the corresponding adducts in up to 99%yield, over 20:1 dr and 81%ee. (2) Based on the work of (1), a highly regio-and enantioselective asymmetric vinylogous Mannich reaction of readily available fluorinated aldimines bearing a chiral auxiliary [(S)-1-phenylethyl group] with siloxyfurans to afford chiral fluorine-containing y-butenolide derivatives in up to 99%yield along with over 20:1 dr and 99%ee has been developed in the presence of silver acetate (10 mol%) and axially chiral phosphine-oxazoline ligand I-I-L1 (11 mol%). (3) Axially chiral phosphine-oxazoline ligand I-I-L6 derived from (R)-binol was identified as a fairly effective chiral ligand in silver(I)-catalyzed asymmetric Mannich reaction of N-Boc aldimines with trimethylsiloxyfuran, giving the corresponding adducts in up to 97%yield,7:1 dr and 86%ee (major diastereoisomer). Since the N-protecting group (N-Boc) can be readily cleaved under several convenient acidic conditions(HCl or TFA), this reaction will be useful in organic synthesis.
Part II:Chiral tertiary amine-or phosphine-catalyzed reactions of electron-deficient allenes with activated alkenes (C=C). (1) D-Threonine-L-tert-leucine-based bifunctional phosphine-catalyzed highly enantioselective [3+2] annulation of allenes with maleimides has been disclosed, affording the corresponding functionalized bicyclic cyclopentenes containing two tertiary stereogenic centers in good to high yields and with good to high enantioselectivities. The plausible reaction mechanism and the further transformation of cycloadducts have been also disclosed. (2) The first example ofβ-ICD catalyzed highly enantioselective intermolecular Rauhut-Currier reaction of maleimides with allenoates and penta-3,4-dien-2-one has been also disclosed, allowing the synthesis of optically active functionalized allene derivatives in good to high yields along with good to excellent enantioselectivities. These chiral functionalized allenic derivatives can be further transformed to the corresponding chiral y-butenolide derivatives and furan derivatives in good yields in the presence of transition metal catalysts.
Part III:Tertiary amine-catalyzed reactions of electron-deficient allenes with activated ketones (C=O). (1) We have developed the first asymmetric organocatalytic formal [2+2] cycloaddition of trifluoromethylketones and allenoates using (3-isocupreidine (β-ICD) as a catalyst to afford S-configured 2-alkyleneoxetanes in moderate to good yields along with good to high diastereoselectivities and enantioselectivities. (2) We have disclosed a 4-(N,N-dimethylamino)pyridine (DMAP)-catalyzed Morita-Baylis-Hillman reaction of isatins with allenoates, affording the corresponding adducts in good to high yields with moderate diastereoselectivities. This is the first example on the Morita-Baylis-Hillman reaction of the carbonyl group in activated ketone with electron-deficient allenic ester.
引文
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