Title

非均相鈦-磺胺基醇錯化物催化不對稱乙基加成醛類反應及鈦-雙萘酚與鈦-雙磺胺基醇催化鏡像選擇三芳香基鋁加成酮類反應

Translated Titles

Heterogeneous Titanium Complexes of N-Sulfonylated Aminoalcohols Catalyzed Asymmetric Ethylation of Aldehydes and Enantioselective Arylation of AlAr3(THF) to Ketones Catalyzed by Titanium Catalysts of (S)-BINOL and Disulfonamide Alcohol

Authors

陳建安

Key Words

不對稱催化 ; 鈦金屬 ; 手性 ; Asymmetric catalysis ; Titanium ; Chirality

PublicationName

中興大學化學系所學位論文

Volume or Term/Year and Month of Publication

2008年

Academic Degree Category

博士

Advisor

高漢謀

Content Language

英文

Chinese Abstract

本研究使用自由基為起始劑對於苯乙烯、二乙烯苯與含苯乙烯單元之雙手性磺胺基醇進行共聚合反應,可成功合成兩種含有雙手性磺胺基醇之聚苯乙烯94與95。聚合物94與95的產率分別為85.8與84.7%,並使用紅外光譜儀與固態核磁共振光譜儀鑑定,經由元素分析儀所測得之數據,可計算每公克聚合物94含有0.93毫莫耳之二牙磺胺基醇單體,而每公克聚合物95則含有0.95毫莫耳之三牙磺胺基醇單體。四異丙烷氧基鈦搭配聚合物94可有效的催化不對稱二乙基鋅加成醛類反應,且此二級醇產物皆可得到大於90%之鏡像超越值,而將其重覆使用9次之後仍可得大於87%之鏡像超越值。四異丙烷氧基鈦搭配聚合物95之催化系統,對於不對稱三乙基鋁加成醛類反應僅能使用1次,且此二級醇產物可得73-92%之鏡像超越值。 鈦-雙萘酚錯化物催化不對稱三芳香基鋁加成酮類反應,在此已被成功的報導出來,並針對一系列的酮類進行測試。在芳香酮中,無論在芳香環的2、3、4位具有推電子或拉電子基,大部分皆可得大於90%之鏡像超越值,當芳香環具有鄰位取代基時,可發現明顯的立體效應,導致需較長的反應時間才可達較高之產率,而此系統也可催化α,β-不飽和酮與2-乙醯基呋喃,並獲得優良之鏡像超越值。此催化系統也可藉由鋁試劑與酮類上之芳香基的調配,進而使用單一組態之配位基即可得互為鏡像異構物之產物。 雙磺胺基醇(116)之鈦錯化物催化不對稱三苯基鋁加成酮類反應,在此已被成功的報導出來。本研究發現溴化鎂在三苯基鋁加成酮類反應中,扮演著一關鍵添加劑之角色,在芳香酮中(除2-甲氧基苯乙酮外),無論在芳香環具有推電子或拉電子基,其三級醇產物皆可得大於90%之鏡像超越值,且鄰位具有取代基時,需拉長反應時間才可獲得較好的產率。基於此催化反應之計量,推測溴化鎂可能扮演著移開鈦金屬錯化物上磺醯胺之氧原子的角色,以空出位置讓酮類能進入反應中心。 本研究測試一系列的苯基加成醛類與酮類之背景、當量與催化量之反應,由1H核磁共振光譜與X光單晶繞射研究,可證實苯基三異丙烷氧基鈦存在此催化系統中,並在催化反應中扮演著關鍵的角色,以獲得卓越之鏡像選擇性。混合雙萘酚二異丙烷氧基鈦與苯基三異丙烷氧基鈦可得Ti2Ph(BINOLate)(O-i-Pr)5 (176),並以X光單晶繞射儀鑑定其結構,觀察此結構可發現一個類似口袋的空間,位在架橋異丙烷氧基的同側,醛類或酮類可從口袋的頂端進入Ti(1)金屬中心,而形成六配位之幾何結構,此時反應物會被放置在適當的位向,進而達到優異的鏡像選擇性。因此,根據實驗證據推測出其催化循環圖,以解釋此系統之不對稱加成醛類與酮類反應。

English Abstract

Two novel cross-linked polystyrene-supported N-sulfonylated β-aminoalcohol resins 94 and 95 have been prepared from radical co-polymerizations of styrene, divinylbenzene, and styrenes bearing a para-substituent of N-sulfonylated aminoalcohol. Resins 94 and 95 were obtained in high yields of 85.8 and 84.7%, and were characterized by IR and solid state 13C NMR spectroscopy. Elemental analyses reveal that one gram of the resin 94 contains 0.93 mmol bidentate N-sulfonylated β-aminoalcohol. The ligand content in the tridentate resin 95 is calculated to be 0.95 mmol/g. The Ti(O-i-Pr)4/94 catalytic system works excellently in asymmetric ZnEt2 additions to aldehydes affording secondary alcohols in ≥90% ee. The resin 94 can be reused 9 times without losing any activity, giving the product with enantioselectivities ≥87% ee. The Ti(O-i-Pr)4/95 system was used only once in asymmetric AlEt3 additions to a variety of aldehydes affording secondary alcohols in good to excellent enantio- selectivities from 73 to 92% ee. Novel asymmetric aryl additions of AlAr3(THF) to ketones catalyzed by the titanium catalyst of (S)-BINOL are reported. A wide variety of ketones are examined to afford products, in general, in excellent enantioselectivities of ≥90% ee for aromatic ketones bearing either an electron-donating or an electron-withdrawing substituent at 2’-, 3’-, or 4’-position on the aromatic ring. Steric effects are found for additions to ortho-substituted aromatic ketones with longer reaction times required to give products in higher yields. The catalytic system applies also to α,β-unsaturated ketones and 2-acetylfuran to give products in good to excellent enantioselectivities. More importantly, aluminum reagents with different aryl nucleophiles can be easily prepared for additions to aromatic ketones furnishing tertiary diaryl alcohols in both absolute configurations. Asymmetric AlPh3(THF) additions to ketones catalyzed by the titanium catalyst of 20 mol% trans-1,2-bis(hydroxycamphorsulfonylamino)cyclohexane (116) are now reported. Several important features were demonstrated in this study. First, a novel aspect of inorganic salt of MgBr2 as a key additive to promote the phenyl addition of AlPh3(THF) to ketones was demonstrated. Second, the catalytic system worked excellently for aromatic ketones bearing either an electron-withdrawing or an electron-donating substituent on the aromatic group to afford tertiary alcohols in enantioselectivities of ≥90% ee except for 2’-methoxyacetophenone. Third, longer reactions times were required for ortho-substituted aromatic ketones to furnish products in good yields. Based on these results, we propose that MgBr2 binds to the sulfonamide oxygen atom, thereby freeing a coordination site for the ketone substrate. A series of background, stoichiometric, and catalytic phenyl addition reactions are tested for aldehydes and ketones. TiPh(O-i-Pr)3 exists in the catalytic system, as confirmed by 1H NMR study and X-ray diffraction. These results indicate that TiPh(O-i-Pr)3 plays a key role in the catalytic reactions, yielding high enantio- selectivities. Ti2Ph(BINOLate)(O-i-Pr)5 (176) is synthesized by mixing Ti(BINOLate)- (O-i-Pr)2 and TiPh(O-i-Pr)3, and characterized by X-ray diffraction. Observation of the structure of complex 176 reveals a pocket on the same side of the bridging isopropoxide. Aldehydes and ketones apparently access the Ti(1) metal center from the top of the pocket to form a six-coordinate metal center, and the substrates then would appear to be placed in the proper orientation for achieving the excellent enantioselectivities. Thus, a catalytic cycle is depicted to illustrate the Ti(O-i-Pr)4/AlPh3(THF) asymmetric catalytic addition reactions with aldehydes or ketones.

Topic Category 基礎與應用科學 > 化學
理學院 > 化學系所
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