Experimental and theoretical studies on the hydrogen-bond-promoted enantioselective hetero-Diels-alder reaction of Danishefsky's diene with benzaldehyde

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	Experimental and theoretical studies on the hydrogen-bond-promoted enantioselective hetero-Diels-alder reaction of Danishefsky's diene with benzaldehyde
	Zhang X(张雪) ; Du HF(杜海峰) ; Wang Z(王正) ; Wu YD(吴云东) ; Ding KL(丁奎岭)
刊名	J. Org. Chem.
	2006
卷号	71 期号:7 页码:2862-2869
ISSN号	0022-3263
其他题名	氢键促进的Danishefsky二烯与苯甲醛对映选择性杂-Diels-alder反应实验及理论研究
通讯作者	吴云东 ; 丁奎岭
英文摘要	The enantioselective hetero-Diels-Alder (HDA) reaction of Danishefsky's diene with benzaldehyde has been achieved catalytically by a series of alpha,alpha,alpha',alpha'-tetraaryl-1,3-dioxolane-4,5-dimethanol (TADDOL) derivatives through hydrogen-bonding activation, affording 2-phenyl-2,3-dihydro-4H-pyran-4-one after trifluoroacetic acid workup in moderate yield and good enantioselectivity. The alpha,alpha'-aryl substituents in the TADDOL molecules are found to exert a significant impact on both the activity and the enantioselectivity of the catalysis. In combination with the experimental investigations, the mechanism of the present reaction has also been studied theoretically using the ONIOM (133LYP/6-31G*:PM3) method with trans-1,3-dimethoxy-1,3-butadiene as the model for Danishefsky's diene. In agreement with the experimental findings, the calculation results indicate that this TADDOL-catalyzed HDA reaction proceeds via a concerted mechanism through an asynchronous and zwitterionic transition structure (TS). The carbonyl group of benzaldehyde is activated by forming an intermolecular hydrogen bond with one of the hydroxy groups of TADDOL. Meanwhile, the intramolecular hydrogen bond between the two hydroxy groups in TADDOL is found to facilitate the intermolecular hydrogen bonding with benzaldehyde. The sense of asymmetric induction is well-rationalized by the analysis of the relative energies of TADDOL-complexed TSs, while the different stereocontrol capabilities exhibited by TADDOLs in the reaction can be qualitatively established on the basis of the structural features of their corresponding TSs.
学科主题	金属有机化学
收录类别	SCI
原文出处	http://dx.doi.org/10.1021/jo060129c
语种	英语
WOS记录号	WOS:000236652200040
公开日期	2013-02-22
内容类型	期刊论文
源URL	[http://202.127.28.38/handle/331003/17825]
专题	上海有机化学研究所_金属有机化学国家重点实验室
推荐引用方式 GB/T 7714	Zhang X,Du HF,Wang Z,et al. Experimental and theoretical studies on the hydrogen-bond-promoted enantioselective hetero-Diels-alder reaction of Danishefsky's diene with benzaldehyde[J]. J. Org. Chem.,2006,71(7):2862-2869.
APA	张雪,杜海峰,王正,吴云东,&丁奎岭.(2006).Experimental and theoretical studies on the hydrogen-bond-promoted enantioselective hetero-Diels-alder reaction of Danishefsky's diene with benzaldehyde.J. Org. Chem.,71(7),2862-2869.
MLA	张雪,et al."Experimental and theoretical studies on the hydrogen-bond-promoted enantioselective hetero-Diels-alder reaction of Danishefsky's diene with benzaldehyde".J. Org. Chem. 71.7(2006):2862-2869.