手性亚磷酸酯—吡啶配体的合成及其在1，4-共轭加成反应中的应用
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摘要
本文从手性NOBIN和手性BINOL出发，设计、合成了一类新型的亚磷酸酯-吡啶配体，并系统地研究了它们在铜(Ⅰ)催化Et_2Zn对α，β-不饱和烯酮的1，4-共轭加成反应中的应用。结果表明：(S)-NOBIN和(S)-BINOL衍生的配体是匹配的，其中BINOL部分的手性对产物的绝对构型起主导作用；配体中吡啶氮参与了与Cu(Ⅰ)的配位，吡啶 6-位的甲基取代基对反应具有明显的影响。配体(S，S)-La对亚苄基丙酮类底物具有较好的手性诱导能力。配体(S，S)-Lc则对取代查耳酮底物表现出更高的对映体选择性，最高ee值达到97.1％，是目前这一反应体系的最好结果之一。
通过对联萘骨架进行部分加氢开发出一类型的H_8-联萘亚磷酸酯-吡啶配体Lk-Lp，它们在Cu(Ⅰ)-催化Et_2Zn对烯酮的1，4-共轭加成反应中的应用表明：(S)-H_8-NOBIN和(S)-BINOL衍生的配体(S,S)-Ll对各种取代查耳酮都取得了很好的ee值；相应的配体(S,S)-Lk则对取代亚苄基丙酮底物表现出很高的手性诱导能力，最高ee值达到97.8％，是目前这一反应体系的最好结果。
配体LA的光学纯度与1，4-共轭加成产物的ee值间呈现明显的正的非线性效应。实验数据符合Kagan的ML_2模型。
在亚磷酸酯-吡啶配体-Cu(Ⅰ)络合物催化的Et_2Zn对烯酮的1，4-共轭加成反应中，观察到随着反应温度的提高加成产物的绝对构型发生了反转。
A new type of phosphite-pyridine ligands derived from chifal NOBESJ and BINOL were designed, synthesized and employed in Cu(I)-catalyzed enantioselective 1,4-conjugate addition of EtiZn to enones. The results demonstrated that the ligands derived from (S)-NOBIN and (S)-BINOL were matched for the high enantioselectivity; the BINOL moiety played a pivotal role in the absolute configuration of the addition products. The nitrogen in pyridine coordinated to the metal center Cu(I) and the 6-Me in pyridine exerted an important effect on the product enantioselectivities. Ligand (S,S)-La afforded good enantioselectivities in the addition reaction of Et2Zn to trans-4-aryl-3-buten-2-one. The ligand (S,S)-Lc was better for chalcones, and up to 97.1 % was achieved. To our knowledge, this was one of the best results in this kind of reactions.
We synthesized a new type of Hg-binaphthyl-phosphite-pyridine ligands Lk-Lp and systematically studied their application in Cu(I)-catalyzed 1,4-conjugate additions of EtaZn to enones. The results showed the ligand (S, S)-Ll derived from (S)-H8-NOBIN and (5)-BINOL backbone afforded high enantioselectivities for various chalcones. The corresponding ligand (S,S)-Lk achieved very high ee values for tans-4-aryl-3-buten-2-one substrates, and up to 97.8 % ee has been obtained.
To the best of our knowledge, this is the best result for the enantioselective 1,4-conjugate addition of Et2Zn to /raw5-4-aryl-3-buten-2-one.
A clear positive nonlinear effect of the enantioselectivity of ligand LA on the product ee was observed in the enantioselective 1,4-conjugate addition. The experimental data met Kagan's MLj model.
We observed a variation of the product absolute configuration with temperature in the Cu(I)-phosphite-pyridine complex catalyzed 1,4-conjugate addition of EtaZn to enones.
通过对联萘骨架进行部分加氢开发出一类型的H_8-联萘亚磷酸酯-吡啶配体Lk-Lp，它们在Cu(Ⅰ)-催化Et_2Zn对烯酮的1，4-共轭加成反应中的应用表明：(S)-H_8-NOBIN和(S)-BINOL衍生的配体(S,S)-Ll对各种取代查耳酮都取得了很好的ee值；相应的配体(S,S)-Lk则对取代亚苄基丙酮底物表现出很高的手性诱导能力，最高ee值达到97.8％，是目前这一反应体系的最好结果。
配体LA的光学纯度与1，4-共轭加成产物的ee值间呈现明显的正的非线性效应。实验数据符合Kagan的ML_2模型。
在亚磷酸酯-吡啶配体-Cu(Ⅰ)络合物催化的Et_2Zn对烯酮的1，4-共轭加成反应中，观察到随着反应温度的提高加成产物的绝对构型发生了反转。
A new type of phosphite-pyridine ligands derived from chifal NOBESJ and BINOL were designed, synthesized and employed in Cu(I)-catalyzed enantioselective 1,4-conjugate addition of EtiZn to enones. The results demonstrated that the ligands derived from (S)-NOBIN and (S)-BINOL were matched for the high enantioselectivity; the BINOL moiety played a pivotal role in the absolute configuration of the addition products. The nitrogen in pyridine coordinated to the metal center Cu(I) and the 6-Me in pyridine exerted an important effect on the product enantioselectivities. Ligand (S,S)-La afforded good enantioselectivities in the addition reaction of Et2Zn to trans-4-aryl-3-buten-2-one. The ligand (S,S)-Lc was better for chalcones, and up to 97.1 % was achieved. To our knowledge, this was one of the best results in this kind of reactions.
We synthesized a new type of Hg-binaphthyl-phosphite-pyridine ligands Lk-Lp and systematically studied their application in Cu(I)-catalyzed 1,4-conjugate additions of EtaZn to enones. The results showed the ligand (S, S)-Ll derived from (S)-H8-NOBIN and (5)-BINOL backbone afforded high enantioselectivities for various chalcones. The corresponding ligand (S,S)-Lk achieved very high ee values for tans-4-aryl-3-buten-2-one substrates, and up to 97.8 % ee has been obtained.
To the best of our knowledge, this is the best result for the enantioselective 1,4-conjugate addition of Et2Zn to /raw5-4-aryl-3-buten-2-one.
A clear positive nonlinear effect of the enantioselectivity of ligand LA on the product ee was observed in the enantioselective 1,4-conjugate addition. The experimental data met Kagan's MLj model.
We observed a variation of the product absolute configuration with temperature in the Cu(I)-phosphite-pyridine complex catalyzed 1,4-conjugate addition of EtaZn to enones.
引文
1 (a) Ojima, Ⅰ. Catalytic Asymmetric Synthesis, 2nd ed.; VCH: Weinheim, Germany, 1999
2 Rossiter, B. E.; Swingle, N. M. Asymmetric conjugate addition, Chem. Rev. 1992, 92, 771-806 and references therein
3 (a) Soia, K.; Okudo, M.; Okamoto, M. Enantioseleetive conjugate addition of diethylzinc to enones using chiral β-aminoalcohol as chiral catalyst or ligand, Tetrahedron Lett. 1991, 32, 95-96. (b) Soai, K.; Hayasaka, T; Ugajin, S.; Asymmetric Synthesis of optically active β-substituted ketones by highly enantioselective catalytic conjugate addition of dialkylzinc reagents to enones using a catalyst system of niekel(Ⅱ)-chiral ligand-aehiral ligand in acetonitrile/toluene, J. Chem. Soc., Chem. Commun. 1989, 516-517. (c)Soai, K.; Yokayama, S.; Hayamaka, T.; Ebihara, K. Catalytic asymmetric induction in enantioselective conjugate addition of dialkylzincs to enones, J. Org. Chem. 1988, 53, 4148-4149. (d) Soai, K.; Hayamaka, Y.; Ugajin, S.; Yokoyama, S. Catalytic enantioselective conjugate addition of dialkylzines to α,β-unsaturated ketones using nickel bromide-N,N-dibutylnorephedrine, Chem. Lett. 1988, 1571-1572
4 (a) Shadakshari, U.; Nayak, S. K. Enantioseleetive conjugate addition of diethylzinc to chalcones catalysed by N-trityl aziridine-2-(S)-(diphenyl)methanol and Ni(acac)_2, Tetrahedron 2001, 57, 8185-8188. (b) Yin, Y.; Li, X.; Lee, D.; Yang, T. Asymmetric conjugate addition of diethylzinc to chalcone catalyzed by nickel complexes containing derivatives of (1R,2S,3R)-3-mercaptocamphan-2-ol, Tetrahedron: Asymmetry 2000, 11, 3229-3333. (c) Spieler, J.; Huttenloch, O.;
Waldmann, H. Synthesis of chiral amino alcohols embodying the bispidine framework and their application as ligands in enantioselectively catalyzed additions to C=O and C=C Groups, Eur. J. Org. Chem. 2000, 391-399. (d) de Vries, A. H. M.; Imbos, R.; Feringa, B. L. (+)-Camphor-derived tri-and tetradentate amino alcohols; synthesis and application as ligands in the nickel catalyzed enantioselective conjugate addition of diethylzinc, Tetrahedron: Asymmetry 1997, 8, 1467-1473. (e) de Vries, A. H. M.; Jansen, J. F. G. A.; Feringa, B. L. Enantioselective conjugate addition of diethylzinc to chalcones catalysed by chiral Ni(Ⅱ) aminoalcohol complexes, Tetrahedron 1994, 50, 4479-4491. (f) Jansen, J. F. G. A.; Feringa, B. L. Catalytic enantioselective conjugate addition of diethylzinc using Ni~Ⅱ-DAIB complexes, Tetrahedron: Asymmetry 1992, 3, 581-582. (g) Bolm, C.; Ewald, M.; Felder, M. Catalytic enantioselective conjugate addition of dialkylzinc compounds to chalcones, Chem. Ber. 1992, 125, 1205-1215. (h) Bolm, C.; Ewald, M. Optically active bipyridines in nickel catalyzed enantioselective conjugate addition to enones, Tetrahedron Lett. 1990, 31,. 5011-5012
5 Alexakis, A.; Frutos, J.; Mangeney, P. Chiral phosphorus ligands for the asymmetric conjugate addition of organocopper reagents, Tetrahedron: Asymmetry 1993, 4, 2427-2430
6 For reviews see: (a) Alexakis, A.; Benhaim, C. Enantioselective copper-catalysed conjugate addition, Eur. J..Org. Chem. 2002, 3221-3236. (b) Krause, N.; Roder. A. H. Recent advances in catalytic enantioselective Michael additions, Synthesis 2001,. 171-196. (c) Feringa, B. L. Phosphoramidites: Marvellous ligands in catalytic asymmetric conjugate addition, Acc. Chem. Res. 2000, 33, 346-353. (d)
Sibi, M. P.; Manyem, S.; Enantioselective conjugate additions, Tetrahedron 2000, 56, 8033-8061. (e) Krause, N. Copper-catalyzed enantioselective Michael additions: Recent progress with new Phosphorus ligands, Angew. Chem., Int. Ed 1998, 37, 283-285. (f) Krause, N.; Gerold, A. Regio-and stereoselective syntheses with organocopper regents, Angew. Chem., Int. Ed. Engl. 1997, 36, 186-204
7 (a) Arnold, L. A.; Imbos, R.; Mandoli, A.; de Vries, A. H. M.; Naasz, R.; Feringa, B. L. Enantioselective catalytic conjugate addition of dialkylzinc reagents using copper-Phosphoramidite complexes; Ligand variation and non-linear effects, Tetrahedron 2000, 56, 2865-2878. (b) Naasz, R.; Arnold, L. A.; Pineschi, M.; Keller, E.; Feringa, B. L. Catalytic enantioselective annulations via 1,4-addition-Aldol cyclization of functionalized organozinc reagents, J. Am. Chem. Soc. 1999, 121, 1104-1105. (c) Feringa, B. L.; Pineschi, M.; Arnold, L. A.; Imbos, R.; de Vries, A. H. M. Highly enantioselective catalytic conjugate addition and tandem conjugate addition-Aldol reactions of organozinc reagents, Angew. Chem., Int. Ed Engl. 1997, 36, 2620-2623. (d) de Vries, A. H. M.; Meetsma, A.; Feringa, B. L. Enantioselective Conjugate addition of dialkylzinc reagents to cyclic and acyclic enones catalyzed by chiral copper complexes of new phosphorus amidites, Angew. Chem., Int. Ed Engl. 1996, 35, 2374-2376
8 Hu, X.; Chen, H.; Zhang, X. Development of new chiral P,N ligands and their application in the Cu-catalyzed enantioselective conjugate addition of diethylzinc to enones, Angew. Chem., Int. Ed. 1999, 38, 3518-3521
9 (a) Degrado, S. J,; Mizutani, H.; Hoveyda, A. H. Efficient Cu-catalyzed asyrmmetric conjugate additions of alkylzincs to trisubstituted cyclic enones, J.
Am. Chem. Soc. 2002, 124, 13362-13363. (b) Mizutani, H.; Degrado, S. J.; Hoveyda, A. H. Cu-catalyzed asymmetric conjugate additions of alkylzinc reagents to acyclic aliphatic enones, J. Am. Chem. Soc. 2002, 124, 779-781. (c) Degrado, S. J.; Mizutani, H.; Hoveyda, A. H. Modular peptide-based phosphine ligands in asymmetric catalysis: Efficient and enantioselective Cu-catalyzed conjugate additions to Five-, Six-, and Seven-membered cyclic enones, J. Am. Chem. Soc. 2001, 123, 755-756
10 (a) Escher, I. H.; Pfaltz, A. new chiral Oxazoline-Phosphite ligands for the enantioselective copper-catalyzed 1,4-addition of organozinc reagents to enones, Tetrahedron 2000, 56, 2879-2888. (b) Knobel, A. K. H.; Escher, I. H.; Pfaltz, A. Enantioselective copper-catalyzed 1,4-addition of organozinc reagents to enones using chiral Oxazoline-Phosphite ligands, Synlett 1997, 1429-1431
11 Shintani, R.; Fu, G. C. Copper-catalyzed enantioselective conjugate addition of diethylzinc to acyclic enones in the presence of planar-chiral Phosphaferrocene-Oxazoline ligands, Org. Lett. 2002, 4, 3699-3702
12 Zhou, H.; Wang, W.-H.; Fu, Y; Xie, J.-H.; Shi, W.-J.; Wang, L.-X.; Zhou, Q.-L. Highly enantioselective copper-catalyzed conjugate addition of diethylzinc to enones using chiral spiro Phosphoramidites as ligands, J. Org. Chem. 2003, 68, 1582-1584
13 (a) Alexakis, A.; Burton, J.; Vastra, J.; Benhaim, C.; Fournioux, X,; van den Heuvel, A.; Leveque, J.-M.; Maze F.; Rosset, S. Synthesis and application of chiral phosphorus ligands derived from TADDOL for the asymmetric conjugate addition of diethyl zinc to enones, Eur. J. Org. Chem. 2000, 4011-4027. (b) Alexakis, A.; Vastra, J.; Burton, J.; Benhaim, C.; Mangeney, P. Asymmetric
conjugate addition of diethyl zinc to enones with chiral phosphorus ligands derived from TADDOL, Tetrahedron Lett. 1998, 39, 7869-7872.
14 (a) Liang, L.; Chan, A. S. C. Copper-catalyzed highly enantioselective 1,4-conjugate addition of trimethylaluminum to 2-eyclohexenone, Tetrahedron Asymmetry 2002, 13, 1393-1396. (b) Liang, L.; Au-Yeung, T. T.-L.; Chart, A. S. C. Highly enantioselective 1,4-addition of diorganozinc reagents to cyclic enones using chiral diphosphite ligands derived from H_8-Binaphthol, Org. Lett. 2002, 4, 3799-3801. (c) Yan, M.; Zhou, Z.-Y.; Chart, A. S. C. Conjugate addition of diethylzinc to α,β-unsaturated lactones catalyzed by copper-phosphite complexes, Chem. Commun. 2000, 115-116. (d) Yah, M.; Chan, A. S. C. Enantioselective conjugate addition of diethylzinc to cyclic enones with chiral aryl diphosphite-copper catalysts, Tetrahedron Lett. 1999, 40, 6645-6648. (e) Yan, M.; Yang, L. W.; Wong, K. Y.; Chan, A. S. C. Enantioselective conjugate addition of diethylzinc to enones catalyzed by a copper complex of chiral aryl diphosphite, Chem. Commun. 1999, 11-12
15 Yamanoi, Y.; Imamoto, T. Methylene-bridged P-chiral diphosphines in highly enantioselective reactions, J. Org. Chem. 1999, 64, 2988-2989
16 Alexakis, A.; Vastra, J.; Mangeney, P.; Acceleration of the conjugate addition of diethyl zinc to enones by either Cu(OTf)_2 or trivalent phosphorus ligands, Tetrahedron Lett. 1997, 38, 7745-7748
17 Alexakis, A.; Burton, J.; Vastra, J.; Mangeney, P. Asymmetric conjugate addition of diethyl zinc to enones with chiral phosphine ligands, Tetrahedron." Asymmetry 1997, 8, 3987-3990
18 Mandoli, A.; Arnold, L. A.; de Vties, A. H. M.; Salvadori, P.; Feringa, B. L. New bidentate chiral phosphorarnidites in copper-catalyzed asymmetric 1,4-addition of diethylzinc to cyclic α,β-enones: Enantioselective tandem 1,4-addition-Aldol reactions with 2-cyclopentenone, Tetrahedron: Asymmetry 2001, 12, 1929-1937
19 For early representative reports on the ligands with H_8-binaphthyl, see: (a) Zhang, F.-Y.; Pai, C.-C.; Chan, A. S. C. Asymmetric synthesis of chiral amine derivatives through enantioselective hydrogenation with a highly effective rhodium catalyst containing a chiral bisaminophosphine ligand, J. A. Chem. Soc. 1998, 120, 5808-5809. (b) Chan, A. S. C; Zhang, F.-Y.; Yip, C.-W. Novel asymmetric alkylation of aromatic aldehydes with triethylaluminum catalyzed by titanium (1,1'-bi-2-naphthol) and titanium-(5,5',6,6',7,7',8,8'-octahydro-1,1'-bi-2-naphthol) complexes, J Am. Chem. Soc. 1997, 119, 4080-4081. (c) Uemura, T.; Zhang, X.; Matsumura, K.; Sayo, N.; Kumobayashi, H.; Ohta, T.; Nozaki, K.; Takaya, H. Highly efficient enantioselective synthesis of optically active carboxylic acids by Ru(OCOCH_3)_2[(S)-H_8-BINAP], J. Org. Chem. 1996, 61, 5510-5516
20 For recent review on the ligands derived from H_8-binaphthyl, see: Au-Yeung, T. T.-L.; Chan, S.-S.; Chan, A. S. C. Partially hydrogenated 1,1,-binaphthyl as ligand scaffold in metal-catalyzed asymmetric synthesis, Adv. Synth. Catal. 2003, 345, 537-555.
21 Zhang, F.-Y.; Chan, A. S. C. Enantioselective conjugate addition of diethylzinc to cyclic enones catalyzed by chiral copper complexes containing a new phosphorus ligand with an H_8-binaphthoxy moiety, Tetrahedron: Asymmetry 1998, 9, 1179-1182
22 Choi, Y. H.; Choi, J. Y.; Yang, H. Y.; Kim, Y. H. Copper-catalyzed conjugate addition on macrocyclic, cyclic, and acyclic enones with a chiral phosphoramidite ligand having a C_2-symmetric amine moiety, Tetrahedron: Asymmetry 2002, 13, 801-804
23 For the application of ligands derived from chiral NOBIN, see: Yuan, Y.; Long, J.; Sun, J.; Ding, K. Dramatically synergetic effect of carboxylic acid additive on tridentate titanium catalyzed enantioselective hetero-Diels-Alder reaction: Additive acceleration and nonlinear effect, Chem. Eur. J. 2002, 8, 5033-5042 and reference 12 therein.
24 (a)胡信全，陈惠麟，张绪穆，铜(Ⅰ)配合物的不对称催化1，4-共轭加成反应，化学学报，2000，9，1163-1167．(b)胡信全，陈惠麟，张绪穆，新型P,N配体及其1,4-共轭加成反应，化学学报，2000，9，1156-1162
25 胡信全，中国科学院大连化学物理研究所1996级博士学位论文，1999
26 (a) Fraser, P. K.; Woodward, S. Highly enantioselective conjugate addition of AlMe_3 to linear aliphatic enones by a designed catalyst, Chem. Eur. J. 2003, 9, 776-783. (b) Bomer, C.; Dennis, M. R.; Sinn, E.; Woodward, S. Copper-catalysed asymmetric 1,4-addition of organozinc compounds to linear aliphatic enones using 2,2'-dihydroxy-3,3'-dithioether derivatives of 1,1'-binaphthalene, Eur. J. Org. Chem. 2001, 2435-2446. (c) Bennett, S. M. W.; Brown, S. M.; Cunningham, A.; Dennis, M. R.; Muxworthy, J. P.; Oakley, M. A.; Woodward, S. Copper-catalysed asymmetric conjugate addition of organometallic reagents to linear enones, Tetrahedron 2000, 56, 2847-2855. (d) Pamies, O.; Net, G.; Ruiz, A.; Claver, C.; Woodward, S. Copper-catalysed asymmetric conjugate addition of organometallic reagents to enones using
S,O-ligands with a xylofuranose backbone, Tetrahedron: Asymmetry 2000, 11, 871-877. (e)Bennett, S. M. W.;Brown, S. M.; Conole, G., Dennis, M. R.;Fraser, P. K.; Radojevic, S.; Mcpartlin, M.; Topping, C. M.; Woodward, S. Catalytic conjugate addition promoted by the copper(Ⅰ)-monothiobinaphthol system. Part 3.~1 Comparison of three thiolate-based catalytic systems, J Chem. Soc., Perkin Trans. 1, 1999, 3127-3132. (f) Bennett, S. M. W.; Brown, S. M.; Muxworthy, J. P.; Woodward, S. Copper-catalysed asymmetric conjugate addition of organometallic reagents to linear enones using thiourethane ligands, Tetrahedron Lett. 1999, 40, 1767-1770
27 Seebach, D.; Jaeshke, G.; Pichota, A.; Audergon, L. Helv. Chim. Acta 1997, 80, 2515 and references cited therein.
28 Keller, E.; Maurer, J.; Naasz, R.; Schader, T.; Meetsma, A.; Feringa, B. L. Tetrahedron." Asymmetry 1998, 9, 2409-2413
29 (a) Alexakis, A.; Benhaim, C.; Rosset, S.; Humam, M. Dramatic improvement of the enantiomeric excess in the asymmetric conjugate addition reaction using new experimental conditions, J. Am. Chem. Soc. 2002, 124, 5262-5263. (b) Alexakis, A.; Rosset, S.; Allamand, J.; March, S.; Guillen, F.; Benhaim, C. Novel biphenol Phosphoramidite ligands for the enantioselecfive copper-catalyzed conjugate addition of dialkyl zincs, Synlett 2001, 1375-1378
30 Alexakis, A.; Benhaim, C.; Foumioux, X.; van den Heuvel, A.; Leveque, J.-M.; March, S.; Rosset, S. Catalytic asymmetric conjugate addition on macrocyclic and acyclic enones. Synthesis of R-(-)-muscone, Synlett 1999, 1811-1813
31 (a) Tanaka, K.; Fu, G C. A versatile new catalyst for the enantioselective isomerization of allylic alcohols to aldehydes: scope and mechanistic studies, J
Org. Chem. 2001, 66, 8177-8186. (b) Tanaka, K.; Qiao, S.; Tobisu, M.; Lo, M.; M.-C.; Fu, G. C. Enantioselective isomerization of allylic alcohols catalyzed by a rhodium/phosphaferrocene complex, J. Am. Chem. Soc. 2000, 122 (40), 9870-9871.
2 Rossiter, B. E.; Swingle, N. M. Asymmetric conjugate addition, Chem. Rev. 1992, 92, 771-806 and references therein
3 (a) Soia, K.; Okudo, M.; Okamoto, M. Enantioseleetive conjugate addition of diethylzinc to enones using chiral β-aminoalcohol as chiral catalyst or ligand, Tetrahedron Lett. 1991, 32, 95-96. (b) Soai, K.; Hayasaka, T; Ugajin, S.; Asymmetric Synthesis of optically active β-substituted ketones by highly enantioselective catalytic conjugate addition of dialkylzinc reagents to enones using a catalyst system of niekel(Ⅱ)-chiral ligand-aehiral ligand in acetonitrile/toluene, J. Chem. Soc., Chem. Commun. 1989, 516-517. (c)Soai, K.; Yokayama, S.; Hayamaka, T.; Ebihara, K. Catalytic asymmetric induction in enantioselective conjugate addition of dialkylzincs to enones, J. Org. Chem. 1988, 53, 4148-4149. (d) Soai, K.; Hayamaka, Y.; Ugajin, S.; Yokoyama, S. Catalytic enantioselective conjugate addition of dialkylzines to α,β-unsaturated ketones using nickel bromide-N,N-dibutylnorephedrine, Chem. Lett. 1988, 1571-1572
4 (a) Shadakshari, U.; Nayak, S. K. Enantioseleetive conjugate addition of diethylzinc to chalcones catalysed by N-trityl aziridine-2-(S)-(diphenyl)methanol and Ni(acac)_2, Tetrahedron 2001, 57, 8185-8188. (b) Yin, Y.; Li, X.; Lee, D.; Yang, T. Asymmetric conjugate addition of diethylzinc to chalcone catalyzed by nickel complexes containing derivatives of (1R,2S,3R)-3-mercaptocamphan-2-ol, Tetrahedron: Asymmetry 2000, 11, 3229-3333. (c) Spieler, J.; Huttenloch, O.;
Waldmann, H. Synthesis of chiral amino alcohols embodying the bispidine framework and their application as ligands in enantioselectively catalyzed additions to C=O and C=C Groups, Eur. J. Org. Chem. 2000, 391-399. (d) de Vries, A. H. M.; Imbos, R.; Feringa, B. L. (+)-Camphor-derived tri-and tetradentate amino alcohols; synthesis and application as ligands in the nickel catalyzed enantioselective conjugate addition of diethylzinc, Tetrahedron: Asymmetry 1997, 8, 1467-1473. (e) de Vries, A. H. M.; Jansen, J. F. G. A.; Feringa, B. L. Enantioselective conjugate addition of diethylzinc to chalcones catalysed by chiral Ni(Ⅱ) aminoalcohol complexes, Tetrahedron 1994, 50, 4479-4491. (f) Jansen, J. F. G. A.; Feringa, B. L. Catalytic enantioselective conjugate addition of diethylzinc using Ni~Ⅱ-DAIB complexes, Tetrahedron: Asymmetry 1992, 3, 581-582. (g) Bolm, C.; Ewald, M.; Felder, M. Catalytic enantioselective conjugate addition of dialkylzinc compounds to chalcones, Chem. Ber. 1992, 125, 1205-1215. (h) Bolm, C.; Ewald, M. Optically active bipyridines in nickel catalyzed enantioselective conjugate addition to enones, Tetrahedron Lett. 1990, 31,. 5011-5012
5 Alexakis, A.; Frutos, J.; Mangeney, P. Chiral phosphorus ligands for the asymmetric conjugate addition of organocopper reagents, Tetrahedron: Asymmetry 1993, 4, 2427-2430
6 For reviews see: (a) Alexakis, A.; Benhaim, C. Enantioselective copper-catalysed conjugate addition, Eur. J..Org. Chem. 2002, 3221-3236. (b) Krause, N.; Roder. A. H. Recent advances in catalytic enantioselective Michael additions, Synthesis 2001,. 171-196. (c) Feringa, B. L. Phosphoramidites: Marvellous ligands in catalytic asymmetric conjugate addition, Acc. Chem. Res. 2000, 33, 346-353. (d)
Sibi, M. P.; Manyem, S.; Enantioselective conjugate additions, Tetrahedron 2000, 56, 8033-8061. (e) Krause, N. Copper-catalyzed enantioselective Michael additions: Recent progress with new Phosphorus ligands, Angew. Chem., Int. Ed 1998, 37, 283-285. (f) Krause, N.; Gerold, A. Regio-and stereoselective syntheses with organocopper regents, Angew. Chem., Int. Ed. Engl. 1997, 36, 186-204
7 (a) Arnold, L. A.; Imbos, R.; Mandoli, A.; de Vries, A. H. M.; Naasz, R.; Feringa, B. L. Enantioselective catalytic conjugate addition of dialkylzinc reagents using copper-Phosphoramidite complexes; Ligand variation and non-linear effects, Tetrahedron 2000, 56, 2865-2878. (b) Naasz, R.; Arnold, L. A.; Pineschi, M.; Keller, E.; Feringa, B. L. Catalytic enantioselective annulations via 1,4-addition-Aldol cyclization of functionalized organozinc reagents, J. Am. Chem. Soc. 1999, 121, 1104-1105. (c) Feringa, B. L.; Pineschi, M.; Arnold, L. A.; Imbos, R.; de Vries, A. H. M. Highly enantioselective catalytic conjugate addition and tandem conjugate addition-Aldol reactions of organozinc reagents, Angew. Chem., Int. Ed Engl. 1997, 36, 2620-2623. (d) de Vries, A. H. M.; Meetsma, A.; Feringa, B. L. Enantioselective Conjugate addition of dialkylzinc reagents to cyclic and acyclic enones catalyzed by chiral copper complexes of new phosphorus amidites, Angew. Chem., Int. Ed Engl. 1996, 35, 2374-2376
8 Hu, X.; Chen, H.; Zhang, X. Development of new chiral P,N ligands and their application in the Cu-catalyzed enantioselective conjugate addition of diethylzinc to enones, Angew. Chem., Int. Ed. 1999, 38, 3518-3521
9 (a) Degrado, S. J,; Mizutani, H.; Hoveyda, A. H. Efficient Cu-catalyzed asyrmmetric conjugate additions of alkylzincs to trisubstituted cyclic enones, J.
Am. Chem. Soc. 2002, 124, 13362-13363. (b) Mizutani, H.; Degrado, S. J.; Hoveyda, A. H. Cu-catalyzed asymmetric conjugate additions of alkylzinc reagents to acyclic aliphatic enones, J. Am. Chem. Soc. 2002, 124, 779-781. (c) Degrado, S. J.; Mizutani, H.; Hoveyda, A. H. Modular peptide-based phosphine ligands in asymmetric catalysis: Efficient and enantioselective Cu-catalyzed conjugate additions to Five-, Six-, and Seven-membered cyclic enones, J. Am. Chem. Soc. 2001, 123, 755-756
10 (a) Escher, I. H.; Pfaltz, A. new chiral Oxazoline-Phosphite ligands for the enantioselective copper-catalyzed 1,4-addition of organozinc reagents to enones, Tetrahedron 2000, 56, 2879-2888. (b) Knobel, A. K. H.; Escher, I. H.; Pfaltz, A. Enantioselective copper-catalyzed 1,4-addition of organozinc reagents to enones using chiral Oxazoline-Phosphite ligands, Synlett 1997, 1429-1431
11 Shintani, R.; Fu, G. C. Copper-catalyzed enantioselective conjugate addition of diethylzinc to acyclic enones in the presence of planar-chiral Phosphaferrocene-Oxazoline ligands, Org. Lett. 2002, 4, 3699-3702
12 Zhou, H.; Wang, W.-H.; Fu, Y; Xie, J.-H.; Shi, W.-J.; Wang, L.-X.; Zhou, Q.-L. Highly enantioselective copper-catalyzed conjugate addition of diethylzinc to enones using chiral spiro Phosphoramidites as ligands, J. Org. Chem. 2003, 68, 1582-1584
13 (a) Alexakis, A.; Burton, J.; Vastra, J.; Benhaim, C.; Fournioux, X,; van den Heuvel, A.; Leveque, J.-M.; Maze F.; Rosset, S. Synthesis and application of chiral phosphorus ligands derived from TADDOL for the asymmetric conjugate addition of diethyl zinc to enones, Eur. J. Org. Chem. 2000, 4011-4027. (b) Alexakis, A.; Vastra, J.; Burton, J.; Benhaim, C.; Mangeney, P. Asymmetric
conjugate addition of diethyl zinc to enones with chiral phosphorus ligands derived from TADDOL, Tetrahedron Lett. 1998, 39, 7869-7872.
14 (a) Liang, L.; Chan, A. S. C. Copper-catalyzed highly enantioselective 1,4-conjugate addition of trimethylaluminum to 2-eyclohexenone, Tetrahedron Asymmetry 2002, 13, 1393-1396. (b) Liang, L.; Au-Yeung, T. T.-L.; Chart, A. S. C. Highly enantioselective 1,4-addition of diorganozinc reagents to cyclic enones using chiral diphosphite ligands derived from H_8-Binaphthol, Org. Lett. 2002, 4, 3799-3801. (c) Yan, M.; Zhou, Z.-Y.; Chart, A. S. C. Conjugate addition of diethylzinc to α,β-unsaturated lactones catalyzed by copper-phosphite complexes, Chem. Commun. 2000, 115-116. (d) Yah, M.; Chan, A. S. C. Enantioselective conjugate addition of diethylzinc to cyclic enones with chiral aryl diphosphite-copper catalysts, Tetrahedron Lett. 1999, 40, 6645-6648. (e) Yan, M.; Yang, L. W.; Wong, K. Y.; Chan, A. S. C. Enantioselective conjugate addition of diethylzinc to enones catalyzed by a copper complex of chiral aryl diphosphite, Chem. Commun. 1999, 11-12
15 Yamanoi, Y.; Imamoto, T. Methylene-bridged P-chiral diphosphines in highly enantioselective reactions, J. Org. Chem. 1999, 64, 2988-2989
16 Alexakis, A.; Vastra, J.; Mangeney, P.; Acceleration of the conjugate addition of diethyl zinc to enones by either Cu(OTf)_2 or trivalent phosphorus ligands, Tetrahedron Lett. 1997, 38, 7745-7748
17 Alexakis, A.; Burton, J.; Vastra, J.; Mangeney, P. Asymmetric conjugate addition of diethyl zinc to enones with chiral phosphine ligands, Tetrahedron." Asymmetry 1997, 8, 3987-3990
18 Mandoli, A.; Arnold, L. A.; de Vties, A. H. M.; Salvadori, P.; Feringa, B. L. New bidentate chiral phosphorarnidites in copper-catalyzed asymmetric 1,4-addition of diethylzinc to cyclic α,β-enones: Enantioselective tandem 1,4-addition-Aldol reactions with 2-cyclopentenone, Tetrahedron: Asymmetry 2001, 12, 1929-1937
19 For early representative reports on the ligands with H_8-binaphthyl, see: (a) Zhang, F.-Y.; Pai, C.-C.; Chan, A. S. C. Asymmetric synthesis of chiral amine derivatives through enantioselective hydrogenation with a highly effective rhodium catalyst containing a chiral bisaminophosphine ligand, J. A. Chem. Soc. 1998, 120, 5808-5809. (b) Chan, A. S. C; Zhang, F.-Y.; Yip, C.-W. Novel asymmetric alkylation of aromatic aldehydes with triethylaluminum catalyzed by titanium (1,1'-bi-2-naphthol) and titanium-(5,5',6,6',7,7',8,8'-octahydro-1,1'-bi-2-naphthol) complexes, J Am. Chem. Soc. 1997, 119, 4080-4081. (c) Uemura, T.; Zhang, X.; Matsumura, K.; Sayo, N.; Kumobayashi, H.; Ohta, T.; Nozaki, K.; Takaya, H. Highly efficient enantioselective synthesis of optically active carboxylic acids by Ru(OCOCH_3)_2[(S)-H_8-BINAP], J. Org. Chem. 1996, 61, 5510-5516
20 For recent review on the ligands derived from H_8-binaphthyl, see: Au-Yeung, T. T.-L.; Chan, S.-S.; Chan, A. S. C. Partially hydrogenated 1,1,-binaphthyl as ligand scaffold in metal-catalyzed asymmetric synthesis, Adv. Synth. Catal. 2003, 345, 537-555.
21 Zhang, F.-Y.; Chan, A. S. C. Enantioselective conjugate addition of diethylzinc to cyclic enones catalyzed by chiral copper complexes containing a new phosphorus ligand with an H_8-binaphthoxy moiety, Tetrahedron: Asymmetry 1998, 9, 1179-1182
22 Choi, Y. H.; Choi, J. Y.; Yang, H. Y.; Kim, Y. H. Copper-catalyzed conjugate addition on macrocyclic, cyclic, and acyclic enones with a chiral phosphoramidite ligand having a C_2-symmetric amine moiety, Tetrahedron: Asymmetry 2002, 13, 801-804
23 For the application of ligands derived from chiral NOBIN, see: Yuan, Y.; Long, J.; Sun, J.; Ding, K. Dramatically synergetic effect of carboxylic acid additive on tridentate titanium catalyzed enantioselective hetero-Diels-Alder reaction: Additive acceleration and nonlinear effect, Chem. Eur. J. 2002, 8, 5033-5042 and reference 12 therein.
24 (a)胡信全，陈惠麟，张绪穆，铜(Ⅰ)配合物的不对称催化1，4-共轭加成反应，化学学报，2000，9，1163-1167．(b)胡信全，陈惠麟，张绪穆，新型P,N配体及其1,4-共轭加成反应，化学学报，2000，9，1156-1162
25 胡信全，中国科学院大连化学物理研究所1996级博士学位论文，1999
26 (a) Fraser, P. K.; Woodward, S. Highly enantioselective conjugate addition of AlMe_3 to linear aliphatic enones by a designed catalyst, Chem. Eur. J. 2003, 9, 776-783. (b) Bomer, C.; Dennis, M. R.; Sinn, E.; Woodward, S. Copper-catalysed asymmetric 1,4-addition of organozinc compounds to linear aliphatic enones using 2,2'-dihydroxy-3,3'-dithioether derivatives of 1,1'-binaphthalene, Eur. J. Org. Chem. 2001, 2435-2446. (c) Bennett, S. M. W.; Brown, S. M.; Cunningham, A.; Dennis, M. R.; Muxworthy, J. P.; Oakley, M. A.; Woodward, S. Copper-catalysed asymmetric conjugate addition of organometallic reagents to linear enones, Tetrahedron 2000, 56, 2847-2855. (d) Pamies, O.; Net, G.; Ruiz, A.; Claver, C.; Woodward, S. Copper-catalysed asymmetric conjugate addition of organometallic reagents to enones using
S,O-ligands with a xylofuranose backbone, Tetrahedron: Asymmetry 2000, 11, 871-877. (e)Bennett, S. M. W.;Brown, S. M.; Conole, G., Dennis, M. R.;Fraser, P. K.; Radojevic, S.; Mcpartlin, M.; Topping, C. M.; Woodward, S. Catalytic conjugate addition promoted by the copper(Ⅰ)-monothiobinaphthol system. Part 3.~1 Comparison of three thiolate-based catalytic systems, J Chem. Soc., Perkin Trans. 1, 1999, 3127-3132. (f) Bennett, S. M. W.; Brown, S. M.; Muxworthy, J. P.; Woodward, S. Copper-catalysed asymmetric conjugate addition of organometallic reagents to linear enones using thiourethane ligands, Tetrahedron Lett. 1999, 40, 1767-1770
27 Seebach, D.; Jaeshke, G.; Pichota, A.; Audergon, L. Helv. Chim. Acta 1997, 80, 2515 and references cited therein.
28 Keller, E.; Maurer, J.; Naasz, R.; Schader, T.; Meetsma, A.; Feringa, B. L. Tetrahedron." Asymmetry 1998, 9, 2409-2413
29 (a) Alexakis, A.; Benhaim, C.; Rosset, S.; Humam, M. Dramatic improvement of the enantiomeric excess in the asymmetric conjugate addition reaction using new experimental conditions, J. Am. Chem. Soc. 2002, 124, 5262-5263. (b) Alexakis, A.; Rosset, S.; Allamand, J.; March, S.; Guillen, F.; Benhaim, C. Novel biphenol Phosphoramidite ligands for the enantioselecfive copper-catalyzed conjugate addition of dialkyl zincs, Synlett 2001, 1375-1378
30 Alexakis, A.; Benhaim, C.; Foumioux, X.; van den Heuvel, A.; Leveque, J.-M.; March, S.; Rosset, S. Catalytic asymmetric conjugate addition on macrocyclic and acyclic enones. Synthesis of R-(-)-muscone, Synlett 1999, 1811-1813
31 (a) Tanaka, K.; Fu, G C. A versatile new catalyst for the enantioselective isomerization of allylic alcohols to aldehydes: scope and mechanistic studies, J
Org. Chem. 2001, 66, 8177-8186. (b) Tanaka, K.; Qiao, S.; Tobisu, M.; Lo, M.; M.-C.; Fu, G. C. Enantioselective isomerization of allylic alcohols catalyzed by a rhodium/phosphaferrocene complex, J. Am. Chem. Soc. 2000, 122 (40), 9870-9871.