氮杂环卡宾催化烯酮与氰基查尔酮的[4+2]不对称环加成反应

doi:10.6023/A14040334

摘要/Abstract

报道了氮杂环卡宾催化烯酮与氰基查尔酮的[4+2]不对称环加成反应. 通过L-焦谷氨酸衍生的大位阻卡宾催化烯酮与氰基查尔酮反应，以良好的产率、良好的顺反选择性和优良的对映选择性得到相应的手性多取代二氢吡喃酮类化合物.

The N-heterocyclic carbene (NHC)-catalyzed enantioselective cycloaddition reactions of ketenes are powerful methods for the synthesis of chiral heterocycles. Followed by the previous reported NHC-catalyzed [2+2] and [4+2] cycloaddtion of ketenes with imines, ketones and various heterodienes, the NHC-catalyzed enantioselective [4+2] cycloaddition of ketenes with α-cyanochalcones was investigated in this paper. In the presence of the bulky N-heterocyclic carbene derived from L-pyrogutamic acid, the reaction of ketenes with α-cyanochalcones went smoothly, giving the corresponding chiral multisubstituted dihydropyranones in good yields with good diastereoselectivities and high enantioselectivities. Initially, several NHCs derived from L-pyrogultamic acids were screened for the reaction. The NHC 4b with bulkyl dimethyl(tert-butyl)silyl group and N-isopropylphenyl performed better than others. The reaction catalyzed by NHCs 4c～4d with a free hydroxyl group gave the dihydropyranones with reversed diastereoselectivity but decreased enantioselectivity. The reaction went well in THF, toluene, dichloromethane or ether, while the one in toluene showed best results. Better yield was reached when the reaction was carried out at 0 or -20 ℃. Under optimized reaction conditions, a variety of aryl(alkyl)ketenes were investigated for the reaction. It was found that both electron-donating and electron-withdrawing groups in the aryl(alkyl)ketene are tolerable for the reaction. The one with electron-withdrawing substituent gave the product in better yield and diastereoselectivity, while the one with electron-donating substituent resulted in better enantioselectivity. The alkyl chain of the ketenes could be ethyl, n-propyl and n-butyl. All the α-cyanochalcones with para-, meta- or ortho-substitutent went well for the reaction. The absolute configuration of resulted dihydropyranone 3e was established by the X-ray analysis of its crystal. The reaction is proposed to initialize with the addition of NHC to ketenes to give the enolate I. The adduct Ⅱ is formed from enolate I and α-cyanochalcone via stepwise Michael addition and cyclization or simultaneous Diels-Alder reaction. The elimination of NHC from adduct Ⅱ gives final dihydropyranone 3.

Key words: N-heterocyclic carbenes, [4+2] cycloaddition, asymmetric catalysis, dihydropyranones

引用此文

孙利辉, 梁志钦, 叶松. 氮杂环卡宾催化烯酮与氰基查尔酮的[4+2]不对称环加成反应[J]. 化学学报, 2014, 72(7): 841-844.

Sun Lihui, Liang Zhiqin, Ye Song. Asymmetric N-Heterocyclic Carbene-catalyzed [4+2] Cycloaddition of Ketenes with α-cyanochalcones[J]. Acta Chimica Sinica, 2014, 72(7): 841-844.

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