烷基锌促进末端炔与亚胺的不对称加成反应研究
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摘要
末端炔对C=O和C=N双键的不对称加成反应是近年来有机合成研究领域的热点之一,本文主要讨论了C2对称β-羟基酰胺类配体的合成及在不对称催化苯乙炔和醛的加成反应中的应用,以及二烷基锌促进的末端炔对手性叔丁基亚磺酰亚胺和对甲基苯磺酰亚胺的不对称加成反应研究。本论文包括以下四个部分：
1.炔丙胺是合成天然产物、药物和复杂有机分子的重要砌块,在天然产物全合成和药物合成中可以作为关键中间体,本章对近年来金属催化的末端炔烃对C=N双键的加成反应研究进行了总结。
2.以天然氨基酸为原料,设计合成了一系列C2对称β-羟基酰胺类手性配体,并将其应用于催化苯乙炔对醛的不对称加成反应,实验发现ZnEt2.Ti(OPr)4和溶剂对催化效果有非常大的影响,经过一系列条件优化,获得了很好的产率(82-94％yield)和较高的ee值(52-98%ee)。
3.首次报道了二乙基锌促进的末端炔对手性叔丁基亚磺酰亚胺的不对称加成合成2-烯基-3-炔基胺。二乙基锌与末端炔首先生成炔基锌,在回流条件下与亚胺进行加成反应得到目标产物,该反应对芳香族及脂肪族的炔和亚胺都有很好的适用性,以最高94%的产率和>99：1的非对映选择性得到了目标产物；通过X-单晶衍射确定了产物的绝对构型；并在对反应机理研究的基础上提出了一个合理的机理。
4.首次报道了二甲基锌和BINOL类配体不对称催化末端炔与对甲基苯磺酰亚胺的加成反应,在最佳条件下,考察了不同炔对芳香族和杂芳香族对甲基苯磺酰亚胺的加成,以很高的产率(51-92％yield)和很好的ee值(82-99%ee)得到了2-烯基-3-炔基胺；通过改变炔的加入顺序实现了两分子不同炔对亚胺加成的选择性问题。
The catalytic addition of terminal alkynes to C=O and C=N double bond is one of the major research endevors in synthetic chemistry over the past decades. In this paper, we mainly discuss the design and synthesis of some new C2-symmetric bis(β-hydroxy amide) ligands and their applications in the enantioselective addition of alkynylzinc to aldehydes, and dialkylzinc promoted asymmetric addition of alkynes to chiral N-tert-butylsulfinylimines and N-tosylaldimines. This thesis is composed of four parts as below:
1. Propargylic amines are highly useful building blocks in organic synthesis. This part provides an overview of the most significant advances in the preparation of propargylic amines via the direct addition of alkynes to imines and carbon nitrogen electrophiles in the presence of metal catalysts or promoters.
2. A series of chiral C2-symmetric bis(β-hydroxy amide) ligands was synthesized via the reaction of isophthaloyl dichloride and amino alcohols derived from L-amino acids. The amount of ZnEt2, Ti(O'Pr)4 and solvents had a strong effect on the asymmetric alkynylation of aldehydes, and the propargyl alcohols were obtained in high yields (82-94% yield) and high enantiomeric excesses (52-98% ee) under optimized conditions.
3. The first direct approach for the asymmetric synthesis of (E)-2-arylidene-1,4-diphenylbut-3-yn-l-amines by addition of alkynylzinc to chiral N-tert-butyl-sulfinylimines was reported. The alkynylzinc was formed in situ from dialkylzinc and terminal alkynes reacted with imines under reflux conditions affording the disired products. Following this methodology, a number combination of various alkynes and imines to give the products with excellent diastereoselectivitis and good yields (up to 92% yield and up to>99:1 dr). The stereochemistry of the compounds was determined by X-ray crystallography. On the basis of a number of experimental observations, we gave an explanation for the new reaction mechanism.
4. We have reported the first procedure for the catalytic enantioselective additon of terminal alkynes to N-tosylaldimines to give N-tosyl-(E)-(2-en-3-ynyl)-amines by using dimethylzinc and BINOL-type ligands. The reaction works with a variety of aromatic and heteroaromatic N-tosylaldimines, and with different alkynes, providing the expected products with good yields (51-92% yield) and high enantiomeric excesses (82-99% ee). In particular, this method could be used to deal with two different alkynes to give diversified products successfully.
1.炔丙胺是合成天然产物、药物和复杂有机分子的重要砌块,在天然产物全合成和药物合成中可以作为关键中间体,本章对近年来金属催化的末端炔烃对C=N双键的加成反应研究进行了总结。
2.以天然氨基酸为原料,设计合成了一系列C2对称β-羟基酰胺类手性配体,并将其应用于催化苯乙炔对醛的不对称加成反应,实验发现ZnEt2.Ti(OPr)4和溶剂对催化效果有非常大的影响,经过一系列条件优化,获得了很好的产率(82-94％yield)和较高的ee值(52-98%ee)。
3.首次报道了二乙基锌促进的末端炔对手性叔丁基亚磺酰亚胺的不对称加成合成2-烯基-3-炔基胺。二乙基锌与末端炔首先生成炔基锌,在回流条件下与亚胺进行加成反应得到目标产物,该反应对芳香族及脂肪族的炔和亚胺都有很好的适用性,以最高94%的产率和>99：1的非对映选择性得到了目标产物；通过X-单晶衍射确定了产物的绝对构型；并在对反应机理研究的基础上提出了一个合理的机理。
4.首次报道了二甲基锌和BINOL类配体不对称催化末端炔与对甲基苯磺酰亚胺的加成反应,在最佳条件下,考察了不同炔对芳香族和杂芳香族对甲基苯磺酰亚胺的加成,以很高的产率(51-92％yield)和很好的ee值(82-99%ee)得到了2-烯基-3-炔基胺；通过改变炔的加入顺序实现了两分子不同炔对亚胺加成的选择性问题。
The catalytic addition of terminal alkynes to C=O and C=N double bond is one of the major research endevors in synthetic chemistry over the past decades. In this paper, we mainly discuss the design and synthesis of some new C2-symmetric bis(β-hydroxy amide) ligands and their applications in the enantioselective addition of alkynylzinc to aldehydes, and dialkylzinc promoted asymmetric addition of alkynes to chiral N-tert-butylsulfinylimines and N-tosylaldimines. This thesis is composed of four parts as below:
1. Propargylic amines are highly useful building blocks in organic synthesis. This part provides an overview of the most significant advances in the preparation of propargylic amines via the direct addition of alkynes to imines and carbon nitrogen electrophiles in the presence of metal catalysts or promoters.
2. A series of chiral C2-symmetric bis(β-hydroxy amide) ligands was synthesized via the reaction of isophthaloyl dichloride and amino alcohols derived from L-amino acids. The amount of ZnEt2, Ti(O'Pr)4 and solvents had a strong effect on the asymmetric alkynylation of aldehydes, and the propargyl alcohols were obtained in high yields (82-94% yield) and high enantiomeric excesses (52-98% ee) under optimized conditions.
3. The first direct approach for the asymmetric synthesis of (E)-2-arylidene-1,4-diphenylbut-3-yn-l-amines by addition of alkynylzinc to chiral N-tert-butyl-sulfinylimines was reported. The alkynylzinc was formed in situ from dialkylzinc and terminal alkynes reacted with imines under reflux conditions affording the disired products. Following this methodology, a number combination of various alkynes and imines to give the products with excellent diastereoselectivitis and good yields (up to 92% yield and up to>99:1 dr). The stereochemistry of the compounds was determined by X-ray crystallography. On the basis of a number of experimental observations, we gave an explanation for the new reaction mechanism.
4. We have reported the first procedure for the catalytic enantioselective additon of terminal alkynes to N-tosylaldimines to give N-tosyl-(E)-(2-en-3-ynyl)-amines by using dimethylzinc and BINOL-type ligands. The reaction works with a variety of aromatic and heteroaromatic N-tosylaldimines, and with different alkynes, providing the expected products with good yields (51-92% yield) and high enantiomeric excesses (82-99% ee). In particular, this method could be used to deal with two different alkynes to give diversified products successfully.
引文
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[9]Zani, L.; Alesi, S.; Cozzi, P. G.; Bolm, C. Dimethylzinc-mediated alkynylation of imines. J. Org. Chem.2006,71,1558-1562.
[10]Blay, G.; Cardona, L.; Climent, E.; Pedro, J. R. Highly enantioselective zinc/binol-catalyzed alkynylation of N-sulfonyl aldimines. Angew. Chem., Int. Ed.2008,47, 5593-5596.
[11](a) Patterson, A. W.; Ellman, J. A. Asymmetric synthesis of a,a-dibranched propargylamines by acetylide additions to N-tert-butanesulfinyl ketimines. J. Org. Chem.2006,77,7110-7112.
(b)Ding, C.-H.; Chen, D.-D.; Luo, Z.-B.; Dai, L.-X.; Hou, X.-L. Highly diastereoselective synthesis of N-tert-butylsulfinylpropargyl- amines through direct addition of alkynes to N-tert-butanesulfinimines. Synlett 2006,1272-1274.
[12](a) Morton, D.; Stockman, R. A. Chiral non-racemic sulfinimines:versatile reagents for asymmetric synthesis. Tetrahedron 2006,62,8869-8905.
(b)Ellman, J. A.; Owens, T. D.; Tang, T. P. N-tert-butanesulfinyl Imines:versatile inter-mediates for the asymmetric synthesis of amines. Acc. Chem. Res.2002,35,984-995.
[13]Liu, G.; Cogan, D. A.; Owens, T. D.; Tang, T. P.; Ellman J. A. Synthesis of enantiomerically pure N-tert-butanesulfinyl imines (tert-butanesulfinimines) by the direct condensation of tert-butanesulfinamide with aldehydes and ketones. J. Org. Chem.1999,64,1278-1284
[14]Reviews on carbometallation, for example:
(a)I. Marek,; N. Chinkov, D. Banon-Tene, In Metal-Catalyzed Cross-Coupling Reactions,2nd edition; de Meijere, A.; Diederich, F., Eds. Wiley-VCH, Weinheim,2004; pp.395.
b) D. Banon-Tenne, I. Marek, In Carbometalation Reactions of Zinc Enolate Derivatives In Transition Metals for Organic Synthesis, Beller, M.; Bolm, C. Eds.; Wiley-VCH, 2004,563.
[15]Noller, C. R. Diehtylzinc. Org. Synth. Coll.1943,2,184-186
[1](a) Noyori, R. Asymmetric Catalysis in Organic Synthesis, Wiley, New York,1994;
(b)Comprehensive Asymmetric Catalysis (Eds.:Jacobsen, E. N.; Pfaltz, E. N.; Yamamoto, H.), Springer, Berlin,1999.
[2](a) Corey, E. J.; Cheng, X.-M. The Logic of Chemical Synthesis; John Wiley & Sons:New York,1988.
(b)Yamada, K.; Tomioka, K. Copper-catalyzed asymme-tric alkylation of Imines with Daalkylzinc and related reactions, Chem. Rev.2008, 108,2874-2886.
[3]Examples of application of propargylic alcohols to the synthesis of natural compounds:
a) Cohen, N.; Lopresti, R. J.; Neukom, C.; Saucy, G.. Asymmetric reductions of alpha. beta.-acetylenic ketones and acetophenone using lithium aluminum hydride complexed with optically active 1,3-amino alcohols J. Org. Chem.1980,45,582-588;
(b)Overman, L. E.; Bell, K. L. Enantiospecific total synthesis of dendrobatid toxin 251D. A short chiral entry to the cardiac-active pumiliotoxin A alkaloids via stereospecific iminium ion-vinylsilane cyclizations. J. Am. Chem. Soc.1981,103,1851-1853;
(c)G. Stork, Nakamura, E. J. A simplified total synthesis of cytochalasins via an intramolecular Diels-Alder reaction. J. Am. Chem. Soc.1983,105,5510-5513;
(d)Trost, B. M.; Hipskind, P. A.; Chung, J. Y. L.; Chan, C. The effect of acetylene substituents on a Pd-catalyzed cycloisomerization. Total synthesis of (-)-Sterepolide and assignment of absolute stereochemistry. Angew. Chem. Int. Ed.1989,28,1502-1504;
(e)Roush,W. R.; Sciotti, R. J. Enantio-selective total synthesis of (-)-Chlorothricolide. J. Am. Chem. Soc.1994,116,6457-6458;
(f)Zhu, G.; Lu, X. A Palladium(Ⅱ)-catalyzed construction of alpha.-Methylene-gamma-butyrolactones in optically activef form. total synthesis of (-)-methylenolactocin. J. Org. Chem.1995,60,1087-1089;
(g) Marshall, J. A.; Borbeau, M. P. Synthesis of enantioenriched propargylic alcohols related to poly-ketide natural products. A comparison of methodologies. Org. Lett. 2003,5,3197-3199.
[4]Examples of application of propargylic amines to the synthesis of natural com-pounds:
(a)Porco, J. A.; Schoenen, F. J.; Stout, T. J.; Clardy, J.; Schreiber, S. L. Transannular Diels-Alder route to systems related to dynemicin A. J. Am. Chem. Soc.1990,112,7410-7411;
(b)Nicolaou, K. C.; Hwang, C.-K.; Smith, A. L.; Wendeborn, S. V. Synthesis of dynemicin A models. J. Am. Chem. Soc.1990,112, 7416-7418;
(c)Yoon, T; Shair, M. D.; Danishefsky, S. J.; Shulte, G K. Experiments directed toward a total synthesis of dynemicin A:A solution to the stereochemical problem. J. Org. Chem.1994,59,3752-3754;
(d)Jiang, B.; Xu, M. Highly enantioselective construction of fused pyrrolidine systems that contain a quaternary stereocenter:Concise formal synthesis of (+)-conessine. Angew. Chem. Int. Ed.2004,43,2543-2546.
(e)Fleming, J. J.; Bois, J. D. A synthesis of (+)-saxitoxin. J. Am. Chem. Soc.2006,128,3926-3927.
[5](a) Shibasaki, M.; Ishida,Y.; Iwasaki, G.; Iimori, T.; 1,3-Dipoles are not the only reactive species in 2-acylaziridine pyrolyses. J. Org. Chem.1987,52,3488-3489;
(b)Iverson, S. L.; Uetrecht, J. P. Identification of a reactive metabolite of terbinafine:insights into terbinafine-induced hepatotoxicity. Chem. Res. Toxicol. 2001,14,175-181;
(c)Gokhale, V. M.; Kulkarni V. M. Comparative molecular field analysis of fungal squalene epoxidase inhibitors. J. Med. Chem.1999,42, 5348-5358.
[6]For reviews on alkynylation of carbonyl compounds, see:
(a)Pu, L. Asymmetric alkynylzinc additions to aldehydes and ketones. Tetrahedron 2003,59,9873-9886;
b) Cozzi, P. G.; Hilgraf, R.; Zimmerman, N. Acetylenes in catalysis:Enantio-selective additions to carbonyl groups and imines and applications beyond. Eur. J. Org. Chem.2004,4095-4105;
(c)Frantz, D. E.; FHssler, R.; Tomooka, C. S.; Carreira, E. M. The discovery of novel reactivity in the development of C-C bond-forming reactions:In situ generation of zinc acetylides with ZnⅡ/R3N. Acc. Chem. Res.2000,33,373-381;
(d)Trost, B. M. Weiss, A. H. The enantioselective addition of alkyne nucleophiles to carbonyl groups. Adv. Synth. Catal.2009,351, 963-983.
(e)Aschwanden, P.; E. M. Carreira in Acetylene Chemistry (Eds.:F. Diederich, P. J. Stang, R. R. Tykwinski), Wiley-VCH,Weinheim,2005, pp.101-138.
[7]Examples of alkynylation of aldehydes:(a) Wolf, C.; Liu, S. Bisoxazolidine-catalyzed enantioselective alkynylation of aldehydes. J. Am. Chem. Soc.2006,128, 10996-10997;
(b)Rajaram,A. R.; Pu, L. Regiospecific hydration of y-hydroxy-α,β-acetylenic esters:A novel asymmetric synthesis of tetronic acids. Org. Lett.2006, 8,2019-2021;
(c)Xu, Z.; Lin, L.; Xu, J.; Yan, W.; Wang, R. Asymmetric addition of phenylacetylene to aldehydes catalyzed by-sulfonamide alcohol-titanium complex. Adv. Synth. Catal.2006,348,506-514;
(d)Emmerson, D. P. G.; Hems,W.
P.; Davis, B. G.Carbohydrate-derived amino-alcohol ligands for asymmetric alkynylation of aldehydes. Org. Lett.2006,8,207-210;
(e)Trost, B. M.; Weiss, A. H.; Wangelin, J. Dinuclear Zn-catalyzed asymmetric alkynylation of unsaturated aldehydes. J. Am. Chem. Soc.2006,128,8-9;
(f)Gao, G.; Wang, Q.; Yu, X. Q.;.Xie, R. G.; Pu, L. Highly enantioselective synthesis of γ-Hydroxy-α,β-acetylenic esters by asymmetric alkyne addition to aldehydes. Angew. Chem. Int. Ed.2006,45,122-125. Examples of alkynylation of ketones:
(g)Lu, G.; Li, X.; Li, Y.-M.; Kwang, F. Y.; Chan, A. S. C. Highly enantioselective catalytic alkynylation of ketones-A convenient approach to optically active propargylic alcohols. Adv. Synth. Catal.2006,348,1926-1933;
(h)Chen, C.; Hong, L.; Xu, Z.-Q.; Liu, L.; Wang, R. Low ligand loading, highly enantioselective addition of phenylacetylene to aromatic ketones catalyzed by schiff-base amino alcohols. Org. Lett.2006,8, 2277-2280.
[8](a) Koradin, C.; Polborn, K.; Knochel, P. Enantioselective synthesis of propargyl-amines by copper-catalyzed addition of alkynes to enamines. Angew. Chem. Int. Ed. 2002,41,2535-2538;
(b)Koradin, C.; Gommermann, N.; Polborn, K.; Knochel, P. Synthesis of enantiomerically Enriched propargylamines by copper-catalyzed addition of alkynes to enamines. Chem. Eur. J.2003,9,2797-2811;
(c)Gommer-mann, N.; Koradin, C.; Polborn, K.; Knochel, P. Enantioselective, copper(Ⅰ)-catalyzed three-component reaction for the preparation of propargylamines. Angew. Chem. Int. Ed.2003,42,5763-5766;
(d)Gommermann, N. Knochel, P. Practical highly enantioselective synthesis of terminal propargylamines. An expeditious synthesis of (S)-(+)-coniine. Chem. Commun.2004,2324-2325;
(e)Gommermann, N.; Knochel, P. Practical highly enantioselective synthesis of propargylamines through a copper-catalyzed one-pot three-component condensation reaction. Chem. Eur J.2006,12,4380-4392;
(f)Taylor, A. M.; Schreiber, S. L. Enantioselective addition of terminal alkynes to isolated isoquinoline iminiums. Org. Lett.2006,8, 143-146;
(g)Aschwanden, P.; Stephenson, C. R.; J.; Carreira, E. M. Highly
enantioselective access to primary propargylamines:4-piperidinone as a convenient protecting group. Org. Lett.2006,8,2437-2440.
[9](a) Wei, C.; Li, C.-J. Enantioselective direct-addition of terminal alkynes to imines catalyzed by copper(Ⅰ) pybox complex in water and in toluene.J. Am. Chem. Soc. 2002,124,5638-5639.
(b)Wei, C.; Mague, J. T.; Li, C.-J. Cu(Ⅰ)-catalyzed direct add-ition and asymmetric addition of terminal alkynes to imines. Proc. Natl. Acad. Sci. U.S.A.2004,101,5749-5754.
(c)Li, C-J. The development of catalytic nucleophilic additions of terminal alkynes in water. Ace. Chem. Res.2010,43, 581-590.
[10]Bisai, A.; Singh, V. K. Enantioselective one-pot three-component synthesis of propergylamines. Org. Lett.2006,8,2405-2408.
[11]Ji, J.-X.; Wu, J.; Chan, A. S. C. Catalytic asymmetric alkynylation of a-imino ester: A versatile approach to optically active unnatural a-amino acid derivatives. Proc. Natl. Acad. Sci. U.S.A.2004,102,11196-11120.
[12]Knopfel, T. F.; Aschwanden, P.; Ichikawa, T.; Watanabe, T.; Carreira, E. M. Readily available biaryl P, N ligands for asymmetric catalysis. Angew. Chem. Int. Ed.2004,43,5971-5973.
[13]Colombo, F.; Benaglia, M.; Orlandi, S.; Usuelli, R.; Celentano, G. Very mild, enantioselective synthesis of propargylamines catalyzed by copper(Ⅰ)-bisimine complexes. J. Org. Chem.2006,71,2064-2070.
[14]Traverse, J. F.; Hoveyda, A. H.; Snapper, M. L. Enantioselective synthesis of propargylamines through Zr-catalyzed addition of mixed alkynylzinc reagents to arylimines. Org. Lett.2003,5,3273-3275.
[15](a) Jiang, B.; Si, Y.-G. Highly enantioselective construction of a chiral tertiary carbon center by alkynylation of a cyclic N-acyl ketimine:an efficient preparation of HIV therapeutics. Angew. Chem. Int. Ed.2004,43,216-218
(b)Zani, L.; Eichhorn, T.; Bolm, C. Dimethylzinc-mediated, enantioselective synthesis of propargylic amines. Chem. Eur. J.2007,13,2587-2600.
(c)Yan, W.; Mao, B.; Zhu,S.; Jiang, X.; Liu, Z.; Wang, R. Asymmetric addition of terminal alkynes to N-(diphenylphosphinoyl)imines promoted by stoichiometric amounts of a proline-derived β-amino alcohol. Eur. J. Org. Chem.2009,3790-3794.
[16]Blay, G.; Cardona, L.; Climent, E.; Pedro, J. R. Highly enantioselective zinc/ BINOL-catalyzed alkynylation of N-sulfonyl aldimines. Angew. Chem. Int. Ed. 2008,47,5593-5596.
[17](a) Ding, C.-H.; Chen, D.-D.; Luo, Z.-B.; Dai, L.-X.; Hou, X.-L. Highly diastereoselective synthesis of N-tert-butylsulfinyl propargylamines through direct addition of alkynes to N-tert-butanesulfinimines. Synlett 2006,1272-1274.
(b) Patterson, A. W.; Ellman, J. A. Asymmetric synthesis of α,α-dibranched propargylamines by acetylide additions to N-tert-butanesulfinyl ketimines. J. Org. Chem.2006,71,7110-7112.
(c)Lettan, R. B.; Scheidt, K. A. Lewis base-catalyzed additions of alkynes using trialkoxysilylalkynes. Org. Lett.2005,7,3227-3230.
[18]Turcaud, S.; Berhal, F.; Royer, J. Diastereoselective alkynylation of N-p-tolyl-sulfinylimines with aluminum acetylides. J. Org. Chem.2007,72,7893-7897.
[19]Wu, T. R.; Chong, J. M. Asymmetric synthesis of propargylamides via 3,3'-disubstituted binaphthol-modified alkynylboronates. Org. Lett.2006,8,15-18.
[20]Gonzalez, A. Z.; Canales, E.; Soderquist, J. A. N-propargylamides via the asymmetric Michael addition of β-alkynyl-10-TMS-9-borabicyclo[3.3.2]decanes to N-acylimines. Org. Lett.2006,8,3331-3334.
[21]Rueping, M.; Antonchick, A. P.; Brinkmann, C. DualCatalysis:A combined enantioselective brφsted acid and metal-catalyzed reaction—metal catalysis with chiral counterions. Angew. Chem. Int. Ed.2007,46,6903-6906.
[22]Lu, Y.; Johnstone, T. C.; Arndtsen, B. A. Hydrogen-bonding asymmetric metal catalysis with α-amino acids:A simple and tunable approach to high enantioinduction. J. Am. Chem. Soc.2009,131,11284-11285.
[23]Armas, P.; Tejedor, D.; Tellado, F. G., Asymmetric alkynylation of imines by cooperative hydrogen bonding and metal catalysis. Angew. Chem. Int. Ed.2010,49, 1013-1016.
[24]Yin, C.; Hui, X.-P.; Xu, P.-F.; Niu, L.-F.; Chen, Y.-F.; Wang, B.-H. Development and application of a new general method for the asymmetric synthesis of (E)-(2-en-3-ynyl)-amines. Adv. Synth. Catal.2009,351,357-362.
[25]Gao, F.; Deng, M.; Qian, C. The effect of coordination on the reaction of N-tosyl imines with diethylzinc. Tetrahedron 2005,61,12238-12243.
[26]Reviews on carbometallation, for example:(a) Marek, I.; Chinkov, N.; Banon-Tene, D. In Metal-Catalyzed Cross-Coupling Reactions,2nd edition; de Meijere, A.; Diederich, F., Eds. Wiley-VCH, Weinheim,2004; pp.395. b) Banon-Tenne, D.; Marek, I. In Carbometalation Reactions of Zinc Enolate Derivatives In Transition Metals for Organic Synthesis, Beller, M.; Bolm, C. Eds.; Wiley-VCH,2004,563.
[27]Noller, C. R. Diethylzinc. Org. Syn. Coll.21943, p.184.
[28]Jennings, W. B.; Lovely, C. J. The titanium tetrachloride induced synthesis of N-phosphinoylimines and N-sulphonylimines directly from aromatic aldehydes Tetrahedron 1991,47,5561-5568.