聯(lián)萘基單齒磷配體不對(duì)稱(chēng)氫化研究進(jìn)展課件

1、聯(lián)萘基單齒磷配體不對(duì)稱(chēng)氫化研究進(jìn)展學(xué)生：王培遠(yuǎn)導(dǎo)師：楊啟華 研究員Seminar II內(nèi)容簡(jiǎn)介背景介紹聯(lián)萘基單齒磷配體的合成與發(fā)展聯(lián)萘基單齒磷配體在烯烴不對(duì)稱(chēng)氫化中的應(yīng)用前景展望手性工業(yè)的稅收總額增長(zhǎng)趨勢(shì)及預(yù)測(cè)(Unit: billion $)生物分子具有手性特征，對(duì)生物體系有活性的藥物往往是單一手性對(duì)映體化合物。手性合成是目前有機(jī)化學(xué)和催化化學(xué)的前沿研究方向。 -Chem. & Eng. News, 2004, Vol 82, No. 24, June 14, 472001年諾貝爾化學(xué)獎(jiǎng)不對(duì)稱(chēng)合成K. Barry SharplessRyoji Noyori野依良治（日本）手性催化氫化反應(yīng) 巴

2、里夏普雷斯（美國(guó)）手性催化氧化反應(yīng) William S. Knowles威廉諾爾斯 (美國(guó))手性催化氫化反應(yīng) 不對(duì)稱(chēng)氫化中常用的雙磷配體人們普遍認(rèn)為手性的雙齒配體與金屬螯和，降低了金屬與磷之間化學(xué)鍵的旋轉(zhuǎn)自由度，在一定程度上增加了催化劑的剛性，從而在手性反應(yīng)中更加利于形成較高的反應(yīng)活性和ee值Chem. Soc. Rev., 2008, 37, 839MonoPhos 合成及演變P(NMe2)3toluene12h, refluxA 28-year-old synthesis of micelle-templated mesoporous silicaA procedure for the p

3、reparation of low-density silica described in a patent filed in 1969 V. Chiola, J.E. Ritsko, C.D. Vanderpool, US Patent 3 556 725, 1971 leads to the formation of solids having all the properties of MCM-41, the ordered mesoporous silica disclosed in 1991 J.S. Beck, C.T.-W. Chu, I.D. Johnson, C.T. Kre

4、sge, M.E. Leonowicz, W.J. Roth, J.W. Vartuli, WO Patent 91/11390, 1991.Tetrahedron: Asymmetry, 1994, 5, 699Microporous Mater. 1997, 10, 283手性配體的合成J. Am. Chem. Soc. 2000, 122, 11539金屬/配體、底物、壓力Adv. Synth. Catal. 2003, 345,308L(S)-a(S)-b(S)-c(S)-d(S)-e(S)-fAngew. Chem., Int. Ed. 2000, 39, 3889Why Are B

5、INOL-Based Monophosphites Such Efficient Ligands in Rh-Catalyzed Asymmetric Olefin HydrogenationInfluence of pressure on the hydrogenation of using Rh(L)2-(cod)BF4 as catalyst.OCH2C6H5oxidative addition of H2 is the rate-determining stepJ. Am. Chem. Soc. 2005, 127, 10305Rh/ligand ratio of 1:2 is opt

6、imalInfluence of Rh/L on the hydrogenation of using Rh(L)2-(cod)BF4 as catalyst.Why Are BINOL-Based Monophosphites Such Efficient Ligands in Rh-Catalyzed Asymmetric Olefin HydrogenationJ. Am. Chem. Soc. 2005, 127, 10305Why Are BINOL-Based Monophosphites Such Efficient Ligands in Rh-Catalyzed Asymmet

7、ric Olefin HydrogenationRu/(L)2遵從鎖鑰匙理論“I think we are far from having a general understanding of asymmetric homogeneous hydrogenation after 30 years of research.” (Thomas Riermeier )J. Am. Chem. Soc. 2005, 127, 10305Zheng Z, et al., Org. Lett. 2003, 5, 4137Zheng Z, et al., J. Org. Chem. 2004, 69, 23

8、55Zheng Z, et al., Tetrahedron: Asymmetry 2004, 15, 2011衣康酸二甲酯-芳基烯酰胺-脫氫氨基酸酯Ee=89-99%“Nothing comes without a hidden cost or flip side.” “Asymmetric catalysis is a great boon but carries with it the problem of having to deal with residual metals.”Chem. & Eng. News, 2005, Vol 83, No. 36, September 5 ,

9、 5固載化：聚合物Tetrahedron Lett. 2006, 47, 4263Tetrahedron Lett., 2006, 47, 426392.3-96.4%ee83.4-96.5%ee85.1-96.5%ee固載化：AlTUD-1Chem. Commun., 2004,24,2830 固載化:介孔材料J. Catal., 2008, 254, 91參考文獻(xiàn)1. Chem. & Eng. News, 2004, Vol 82, No. 24, June 14, 47.2. Eberhardt, L. et al. Chem. Soc. Rev., 2008, 37, 839.3. R

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