The 1, n-Rearrangement of a Sulfonyl group and its Utilization for Synthesis of Conjugated

1、磺酰基的正位重排及其在共轭化合物合成中的应用

• 批准号: 02650598
• 负责人: OGURA Katsuyuki
• 金额: $ 1.22万
• 依托单位: Chiba University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02650598/
• 关键词: Sulfonyl Group; 1, n-Rearrangement; Conjugated Polyenes; Conjugated Enone; Conjugated Dienal; Conjugated Trienone; Conjugated Trienal; Conjugated Tetraene; チオ基; 脱離ー再結合; 反応機構; 共役ジエノン; 共役ジエナ-ル

This project is to extend the 1, 3-rearrangement of a sulfonyl group in a sulfenylated allylic system to l, n-rearrangement which is applied to a new and convenient synthesis of conjugated polyenyni carbonyl compounds. At first, polyenes having methylthio and p-tolylsulfonyl groups at alpha position[2 ; R^2(MeS)(PToISO_2)C(CH=CH)mR^1 are derived from easily available methylthiomethyl P-tolyl sulfone(1). Treatment of these polyenes(2)with weak acids such as silica gel is expected to induce I. n-rearrangement of the sulfonyl group leading to 1-methylthio-n-(p-tolylsulfonyl)alkapolyenes[3 ; R^2(MeS)CH=CH(CH=CH)_<m-1>CH(PTolSO_2)R^1 which are synthetic precursors. of polyenyl carbonyl compounds. During the present project, the cases of n = 5, 7, and 9(m = 2, 3. and 4, respectively)were investigated.1. Preparation of the precursor(2)for I. n-rearrangement of a sulfonyl group : The anion of a trimethylsilylated I reacted with unsaturated aldehydes to afford 1-methylthio-l-(p-tolylsulfonyl)al … More kapolyenes[4 ; (MeS)(P-TolSO_2)C=CH(CH=CH)_<m-1>CH_2R^l. When 4 was treated with potassium t-butoxide in THF, an anion was generated. Protonation or alkylation(treatment with an alkyl halide)of the anion gave 2(R^2 =H and alkyl, respectively). As unsaturated aldehydes, 2-enal, 2.4-dienal. and 2, 4, 6-trienal could be utilized.2.1, n-Rearrangement of a sulfonyl group in 2 and synthesis of conjugated polyenones and polyenals : Elution of 2(m = 2 and 3)through column packed with silica gel gave the rearrangement product(3 ; m = 2 and 3, respectively). On similar treatment of 2(m = 4), the 1, 9-rearrangement of a sulfonyl group took place, but the yield was relatively low. Good yield of 3(m = 4)was attained by stirring of 2(m = 4)along with a small amount of silica gel in chloroform. The mechanism of the l. n-rearrangements was also investigated in a detail to reveal that the sulfonyl group dissociates as a sulfinate ion and recombine again with the resulting polyenyl cation.The expected polyenyl carbonyl compounds were obtained by alkylation of 3 with NaH and an alkyl halide followed by hydrolysis with hydrochloric acid. Less

本项目是将磺化烯丙基体系中磺酰基的1,3重排扩展到1，n重排，并应用于一种新的、方便的共轭多烯羰基化合物的合成。首先，在α位置具有甲基硫和对甲基磺酰基的多烯[2]；R^2(MeS)(PToISO_2)C(CH=CH)mR^1是由容易获得的甲基硫甲基对甲基磺基砜(1)衍生而来。用弱酸（如硅胶）处理这些多烯(2)，预计会引起磺酰基的i -n重排，导致1-甲基硫-n-（对甲基磺酰基）烷聚烯[3]；R^2(MeS)CH=CH(CH=CH)_<m-1>CH(PTolSO_2)R^1是合成前体。聚乙烯基羰基化合物。在本项目中，n = 5,7,9 （m = 2,3）的情况。和4)分别进行了调查。I的前驱体(2)的制备：磺酰基的n重排：三甲基硅基化I的阴离子与不饱和醛反应得到1-甲基硫- 1-（对甲基磺酰基）al…更多的卡多烯[4]；(MeS) (P-TolSO_2) C = CH (CH = CH) _ < m - 1 > CH_2R ^ l。当4在THF中与t-丁氧化钾处理时，产生一个阴离子。阴离子的质子化或烷基化（用烷基卤化物处理）得到2（R^2分别=H和烷基）。作为不饱和醛，2-烯醛，2.4-二烯醛。2.1、2中一个磺酰基的n-重排及共轭多烯酮和多烯醛的合成：用硅胶填充柱洗脱2（m = 2和3）得到重排产物（m = 2和3）。在类似的处理2（m = 4）上，发生了磺酰基的1,9重排，但产率相对较低。用2（m = 4）和少量硅胶在氯仿中搅拌，得到了3（m = 4）的好产率。l. n-重排的机理也被详细地研究了，揭示了磺酰基作为亚磺酸离子解离，并再次与产生的多烯基阳离子重新结合。用钠和卤化物将3烷基化，然后用盐酸水解，得到了预期的聚烯基羰基化合物。少

项目成果

Nobuhiro Yarata: "A New and Convenient Preparation of Conjugated Dienals" Bulletin of Chemical Society of Japan. 63. 3601-3605 (1990)

Nobuhiro Yarata：“一种新型且方便的共轭二烯醛制备方法”日本化学会会刊。

Katsyuki Ogura: "A Novel 1,5ーRearrangement of a Sulfonl Group in a 1ーSulfenylate 2,4ーalkadiene" Tetrahedron Lett.31. 4621-4624 (1990)

Katsyuki Ogura：“1-磺酰基 2,4-链二烯中磺基的新型 1,5-重排”Tetrahedron Lett.31 (1990)。

Nobuhiro Nahata, Makoto Fujita, and Katsuyuki Ogura: "A New and Convenient Preparation of Conjugated Dienals" Bull. Chem. Soc. Jpn.63-12. 3601-3605 (1990)

Nobuhiro Nahata、Makoto Fujita 和 Katsuyuki Ogura：“一种新的、方便的共轭二烯醛制备方法”公牛。

Katsuyuki Ogura: "How Does the Conbination of a Thio Group and a Sulfonyl Gorup Contribute to Organic Synthesis?" Reviews on Heteroatom Chemistry.5. 85-112 (1991)

Katsuyuki Ogura：“硫代基团和磺酰基团的结合如何有助于有机合成？”

Katsuyuki Ogura: "How Does the Combination of a Thio Group and a Sulfonyl Group Contribute to Organic Synthesis?" Review on Heteroatom Chemistry. 5-1. 85-112 (1991)

Katsuyuki Ogura：“硫代基团和磺酰基的组合如何有助于有机合成？”