Development and Synthetic Application of a Novel Type of α-Phosphonocyclobutanones and α-Phosphonoazetidinones

新型α-膦酰环丁酮和α-膦酰氮杂环丁酮的开发及合成应用

• 批准号: 10650856
• 负责人: OKADA Yoshiharu
• 金额: $ 2.24万
• 依托单位: Kinki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10650856/
• 关键词: α-Phosphonocyclobutanone; Intramolecular C-H Insertion Reaction; Chiral Rhodium(II) Catalyst; Anthracene; α-Diazo-β-ketophosphonate; Diels-Alder Reaction; 酢酸ロジウム

Recently, the rhodium(II)-catalyzed intramolecular C-H insertion of α-diazo carbonyl compounds has been widely studied and found to be great of value. Reported herein is the synthesis of α-phosphonocyclobutanones bearing 9,10-dihydro-9,10-ethanoanthracene moiety via rhodium(II)-catalyzed intramolecular insertion reaction. 11-Methyl- (3b), 11-ethyl- (3c), and 11-propyl-11-(dimethylphosphono)-acetyl-9,10-dihydro-9,10-ethanoanthracene (3d) were prepared from the Diels-Alder adducts of anthracene and methyl acrylate derivatives, and dimethyl lithiomethylphosphonate in good yields. Α-Diazo β-keto phosphonates 4b-d were readily prepared from 3b-d according to the conventional diazo transfer method by the use of p-toluenesulfonyl azide. Catalytic decomposition of f4b-d was carried out in ClCHィイD22ィエD2CHィイD22ィエD2Cl containing RhィイD22ィエD2(Oac)ィイD24ィエD2 at 80℃ to afford the mixture of cyclobutanones 5b-d and cyclopentanones 6c,d. The stereochemical assignment of 7,8 : 9,10-dibenzo-2-ethyl-4-(dimethylphosphono)tricyclo[4.2.2.0ィイD22,5ィエD2]deca-7,9-dien-3-one (5c) was made on the basis of their ィイD11ィエD1H NMR and IR spectral data. That is, the IR spectrum of 5c shows a peak for carbonyl absorption at 1774.7 cmィイD1-1ィエD1. The ィイD11ィエD1H NMR spectrum of 5c shows a signal for methyl (t, J=4.9 HィイD2ZィエD2, 3H) at δ1.09 and a signal for methine (d, J=3.9 HィイD2ZィエD2, 1H) of 6-position at δ4.51. Accordingly, cyclobutanones were exclusively produced via insertion into the ethane bridge methylene C-H bonds. A similar decomposition of 4b-d with chiral Rh(II) catalysts, such as RhィイD22ィエD2[N-Phtn-(L)-Phe]ィイD24ィエD2 and RhィイD22ィエD2[N-Phth-(L)-Ala]ィイD24ィエD2, afforded the desired optically active 5b-d up to 43%ee. In this reaction, the use of RhィイD22ィエD2[N-Phth-(L)-Phe]ィイD24ィエD2 gave the optically active 5b-d in higher optical yield than that of RhィイD22ィエD2[N-Phth-(L)-Ala]ィイD24ィエD2 irrespective of the kind of alkyl substituents at 11-position of diazo compounds 4b-d.

近年来，Rh(II)催化的α-重氮羰基化合物分子内C-H插入反应得到了广泛的研究，具有很大的应用价值。本文报道了通过Rh(II)催化的分子内插入反应，合成了含9，10-二氢-9，10-乙基蒽环的α-膦环丁酮。11-甲基-(3b)，11-乙基-(3c)，11-乙基-(3c)，11-propyl-11-(dimethylphosphono)-acetyl-9，10-dihydro-9，10-ethanoanthracene(3d)是由菲和丙烯酸甲酯与二甲基硫代甲基膦酸二甲酯的Diels-Alder加合物合成的，产率很高。以3b-d为原料，采用对甲苯磺酰叠氮重氮转移法制备了Α-重氮β-酮基膦酸酯4b-d。7，8：9，10-dibenzo-2-ethyl-4-(dimethylphosphono)tricyclo[4.2.2.0ィイD22，5ィエD2]deca-7，9-dien-3-one(5c)在ィイD22ィエD2CHィイD22ィエD2Cl(RhィイD22ィエD2(OAc)ィイD24ィエD2)中于80℃下催化分解得到环丁酮5b-d和环戊酮6c，d的混合物，并根据其ィイD11ィエD1H核磁共振和红外光谱数据进行了立体化学归属。也就是说，5c的红外光谱在1774.7 cmィイd1-1ィエd1处有一个羰基吸收峰。5c的ィイD11ィエD1H核磁共振谱显示甲基(t，J=4.9HィイD2ZィエD2，3H)在δ1.09处有信号，亚甲基(d，J=3.9HィイD2ZィエD2，1H)在δ4.51处有信号。因此，环丁酮仅通过插入乙烷桥亚甲基C-H键来生成。用手性Rh(II)催化剂，如RhィイD22ィエD2[N-Phtn-(L)-Phe]ィイD24ィエD2和RhィイD22ィエD2[N-phth-(L)-Ala]ィイD24ィエD2对4b-d进行类似的分解，得到了高达43%ee的光学活性5b-d。在该反应中，使用RhィイD22ィエD2[N-phth-(L)-Phe]ィイD24ィエD2得到的光学活性5b-d高于RhィイD22ィエD2[N-phth-(L)-Ala]ィイD24ィエD2，而与重氮化合物4b-d的11位烷基取代基无关。