N-水楊基-L-叔亮胺酸衍生的手性氧釩錯合物催化α-和β-酮醯胺的不對稱還原

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研究生：	拉麒 RACHIT, AGARWAL
論文名稱：	N-水楊基-L-叔亮胺酸衍生的手性氧釩錯合物催化α-和β-酮醯胺的不對稱還原 Asymmetric Reduction of α- and β-Keto Amides Catalyzed By Chiral Oxovanadium Complexes derived from N-Salicylidene-L-tert-Leucine
指導教授：	陳建添 Chen, Chien-Tien
口試委員:	陳貴通 Tan, Kui-Thong 林民生 Hayashi, Tamio 吳學亮 Wu, Hsyueh-Liang 謝仁傑 Hsieh, Jen-Chieh
學位類別：	博士 Doctor
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2021
畢業學年度：	109
語文別：	英文
論文頁數：	451
中文關鍵詞：	不對稱還原、手性氧釩錯合物、α-酮醯胺、β-酮醯胺、α-取代 β-酮醯胺
外文關鍵詞：	Asymmetric reduction, Chiral Oxo-Vanadium Complexes, α--keto amide, β-keto amide, α-substituted β-keto amide
相關次數：	點閱：1 下載：0
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本實驗室以先前開發的3,5-雙取代-N-叔亮胺酸之手性氧釩錯合物，藉由頻哪醇硼烷 (pinacolborane, HBpin) 及兒茶酚硼烷(catecolborane, HBcat) 不對稱催化還原 α-酮基醯胺，擁有不錯的效率。在十二種不同溶劑及六種不同的C3、C5取代的催化劑中，以C3為叔丁基取代，C5為溴取代的氧釩錯合物 1a’，在 −20 ℃ 下以甲苯為溶劑可得到最佳結果。在使用高效的頻哪醇硼烷作為不對稱催化還原試劑，得到產率 44–90% ，鏡像選擇性74–94% (R)；若使用兒茶酚硼烷作為不對稱催化還原試劑，則可得到產率 69–99%，鏡像選擇性60–90% (S)。在預測的過度態中，α-酮基醯胺會因為酮類的羰基與醯胺的氫形成分子內氫鍵，而呈現s-trans構型。因此，頻哪醇硼烷的氫陰離子會從酮類的Si-face攻打，進而還原成R-構型的醇類產物。相反的，因為兒茶酚硼烷的苯環與受質的苯甲醯基片段會產生 π-π 交互作用力，受質會傾向s-cis構型，進而生成S構型的醇類產物。
在第二部分中，我們將受質改為 N-苯甲基-β-酮基醯胺。在九種不同溶劑、三種不同的醇類添加物及四種不同的C3、C5取代的催化劑中，以C3為 2,5-二甲基苯基取代，C5為溴取代的水楊酸衍生之氧釩錯合物 1d，在 −20 ℃ 下以四氫呋喃為溶劑，以頻哪醇硼烷作為還原劑，並搭配叔丁醇做為添加物可得到最佳結果。對應的β-S-羥基醯胺產物，得到產率43–92% ，鏡像選擇性79–99% 。而合成可做為度洛西汀的前驅物，亦可得到產率45% 及鏡像選擇性90% 。對此我們提出兩種還原的過渡態。在模型一中，立體障礙大的頻哪醇硼烷會鍵結在與釩相連接的甲氧基上，並從Re-face提供氫陰離子，得到S構型的醇類產物。另一方面，在模型二中，頻哪醇硼烷會先與V=O鍵結作用，使得氫陰離子從Re-face攻擊在赤道向與釩鍵結的羰基，得到S-構型的醇類產物。
在最後一部分，我們將受質延伸為α-甲基-β-酮基醯胺。在十種不同溶劑、五種不同的添加物及九種不同的C3、C5取代的催化劑中，以氧釩錯合物 1d，在 −20 ℃ 下以等比例之四氫呋喃-丙酮混合溶劑，頻哪醇硼烷作為還原劑，可得到最佳結果為產率70% 、鏡像選擇性91% 及非對映異構選擇性99：1 (同向:反向)。此外，在更具挑戰性的受質α-苯基-β-酮基醯胺，其還原產物α-苯基-β-羥基醯胺得到產率66% 及鏡像選擇性89% 。我們預測以上兩種受質與β-酮基醯胺有類似的過渡態，頻哪醇硼烷會與釩相連接的甲氧基或V=O鍵結作用，使得氫陰離子從Re-face攻擊在赤道向與釩鍵結的羰基，得到高度同向選擇性之α-甲基(或苯基)-β-羥基醯胺。

We have developed an efficient system for the complementary asymmetric reduction of α-ketobenzylamide with pinacolborane (HBPin) and catecholborane (HBCat) catalyzed by chiral oxo-vanadium (V) methoxides complexes derived from 3,5-disubstituted-N-salicylidene-tert-leucine. Among twelve different solvents and six different C-3, C-5 substituted catalysts examined, the use of C3 t-butyl and C-5 Br (1a') catalyst in toluene at −20 °C afforded the best results. An efficient reagent based complementary enantioselective reduction was afforded in 44–90% yield with 74–94% R-isomer using HBPin and 69–99% yield with 60–90% S-isomer using HBCat. In the proposed transition state, the α-ketoamide adopted an s-trans conformation with an internal H-bonding between the ketone carbonyl and the amide H so that the bulky pinacolborane would deliver the hydride from Si-face of the ketone moiety to give the resulting alcohol in R-configuration. Conversely, an s-cis conformation would be preferred in the reduction by catecholborane in view of the favourable - interaction between the benzoyl unit in the substrate and the benzene ring in HBCat to give the resulting alcohol in S-configuration.
In Part 2, we changed the substrate class to N-benzyl-β-ketoamides. Among nine different solvents, three different alcohol additives, and four different catalysts examined, the use of 1d complex bearing 3-(2,5-dimethylphenyl),5-Br on salicylidene template and HBPin as reducing agent in tetrahydrofuran (THF) with a t-BuOH additive led to the best results at −20 °C. The corresponding β-S-hydroxyamides furnished with 43–92% yields and 79–99% ees. A precursor to duloxetine drug has been synthesized in 45% yield and 90 % ee. Two reductant-directed favourable transition state has been proposed, in mode I the bulky HBPin directed by vanadyl bound methoxide delivered the hydride from re face to give S-configuration alcohol. On the other hand, in mode II the HBPin first interact with V=O followed by re face attack on equatorially coordinated carbonyl to give S-configuration alcohol.
In final part, we further extended the substrate class to α-methyl-β-keto amide. A thorough screening of ten solvents, five additives and nine different catalysts afforded the highly desymmetric α-methyl-β-hydroxy amide in 70% yield with 91% ee and 99:1 dr (syn:anti) in THF: acetone (1:1) mixed solvent at −20 °C using HBPin as reducing agent with 1d catalyst. Subsequently, a more challenging α-phenyl-β-ketoamide enantioselectively reduced to syn selective α-phenyl-β-hydroxy amide in 66% yield with 89% ee. A similar plausible transition state has been proposed as that of beta-keto amide, in which bulky HBPin directed by vanadyl bound methoxide or V=O delivered the hydride from re face of carbonyl to give highly syn selective α-methyl/phenyl-β-hydroxy amides.

TABLE OF CONTENTS
Page
中文摘要    i
Abstract    iii
Acknowledgement    v
Table of contents      vii
ABBREVIATIONS   xi
List of Publications    xiii
CHAPTER 1: Introduction    1
Section 1.1. Vanadium    1
Section 1.2. Application of vanadyl complexes in organic synthesis and catalytic reactions.    1
Section 1.2.1. Asymmetric oxidation of secondary alcohol compounds catalyzed by vanadyl complexes    2
Section 1.2.2 Asymmetric coupling reaction of aromatic phenols catalyzed by vanadyl complexes    5
Section 3: Asymmetric reduction    12
1.3.1. Introduction to reducing agent    12
1.3.2 Chiral Oxazaborolidine asymmetric reduction    13
1.3.3 Asymmetric reduction with transition metal complexes and borohydrides or borane derivatives    17
1.3.4 Asymmetric reduction with transition metal complexes and silane derivatives    26
1.3.5 Asymmetric reduction of keto esters and keto amides    31
Chapter 2 Results and discussions    37
Section 2.1 Asymmetric reduction of alpha keto amides    37
2.1.1 Solvent screening    38
2.1.2 Reducing Agent screening    39
2.1.3 Catalyst Screening    40
2.1.4 Additive and solvent screening    42
2.1.5 Substrate Scope    44
2.1.6 Proposed Transition State:    49
2.1.7 Conclusion    50
Section 2.2 Asymmetric reduction of β-keto amides    51
2.2.1 Reducing agent and Solvent Screening    51
2.2.2 Additive screening    52
2.2.3 Catalyst and further solvent screening    53
2.2.4 Substrate Scope    55
2.2.5 Application
2.2.6. Non-Linear Effect study:    58
59
2.2.7 Proposed transition state    62
2.2.8 Conclusion:    63
Section 2.3 Asymmetric reduction of α-substituted-β-ketoamides    64
2.3.1 Additive screening    64
2.3.2 Solvent screening    65
2.3.3 Catalyst Screening    67
2.3.4 Asymmetric reduction of β-keto-α-phenyl substrate:    70
2.3.5 Proposed transition state    71
2.3.5 Conclusion    72
Materials and Methods:    73
Chapter 3 Experimental Section:    75
3.1. Synthesis and characterization data of oxo-vanadium(V) complexes 1a–1l.    75
3.1.1. Synthetic steps and spectral data of 1a catalyst:    75
3.1.2. Synthetic steps and spectral data of 1a’ catalyst:    78
3.1.3. Synthetic steps and spectral data of 1b catalyst:    80
3.1.4. Synthetic steps and spectral data of 1c catalyst:    81
3.1.5. Synthetic steps and spectral data of 1d catalyst:    80
3.1.6. Synthetic steps and spectral data of 1e catalyst:    85
3.1.7. Synthetic steps and spectral data of 1f catalyst:    88
3.1.8. Synthetic steps and spectral data of 1g catalyst:    89
3.1.9. Synthetic steps and spectral data of 1h catalyst:    91
3.1.10. Synthetic steps and spectral data of 1i catalyst:    93
3.1.11. Synthetic steps and spectral data of 1j catalyst:    96
3.1.13. Synthetic steps and spectral data of 1k catalyst:    99
3.1.14. Synthetic steps and spectral data of 1l catalyst:    102
3.2. Synthetic procedure and characteristic data of α-keto amides:    103
3.2.1 Method (a)    103
3.2.2 Method (b) (3b–r)        103
3.3. Reaction procedure for the asymmetric reduction of N-benzyl-α-keto-amides.    109
3.4. General synthetic schemes for the preparation of β-keto amides.    118
3.4.1 Method-a:    118
3.4.2 Method-b:    119
3.4.3 Method-c:    120
3.4.4 Synthesis of N-methyl-3-oxo-3-(thiophen-2-yl)propanamide:    121
3.4.5 Synthesis of N-benzyl-3-oxo-5-phenylpentanamide:    122
3.5. General reaction procedure for the asymmetric reduction of β-keto amides:    123
3.6. Reaction procedure for the synthesis of the (S)-duloxetine precursor: (S)-3-hydroxy-N-methyl-3-(thiophen-2-yl)propanamide:    124
3.7. General procedure for deuterium exchange reaction:    124
3.8. Characterization data of the β-keto amide substrates and products:    125
3.9 Procedure for 2 mmol Scale preparation of (S)-N-Benzyl-3-(4-chlorophenyl)-3-hydroxypropanamide (5d):    140
3.10. Synthetic procedure for for N-benzyl-α-methyl/phenyl-β-keto amides    142
Method a:    142
Method b:    143
3.11. Reaction procedure for the synthesis of racemic α-methyl-β-hydroxy amides:    144
3.12. Reaction procedure for the synthesis of racemic α-phenyl-β-hydroxy amides:    144
3.13. General reaction procedure for the asymmetric reduction of α-methyl-β-keto amides:    145
3.14. Reaction procedure for the asymmetric reduction of α-phenyl-β-keto amides:    146
References    148
HPLC Chromatograms    S1
NMR Spectra    S43
X-ray Data    S269

                                

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