A Study on Intermolecular and Intramolecular Cycloaddition Reactions of Heteroatom-Containing Unsaturated Compounds

含杂原子不饱和化合物分子间和分子内环加成反应的研究

• 批准号: 05640615
• 负责人: SATITO Takao
• 金额: $ 0.77万
• 依托单位: SCIENCE UNIVERSITY OF TOKYO
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05640615/
• 关键词: Thiocarbonyl Compound; Thiocarbonyl Ylide; Ortho-quinodimethane; Conjugated Carbodiimide; Thiaphosphole; Michael Addition Reaction; Diels-Alder Reaction; Electrocyclization; チアブタジエン; ジヒドロキナゾリン; 共役チオケトン; ヘテロディールス・アルダー反応; 分子内ディールス・アルダー反応

1. The alpha, beta : gamma, delta-thiocarbonyl compounds derived from 2-(phenylthio)tetralinethione reacted thermally or in the presence of a Lewis acid catalyst with a variety of dienophiles to afford the polycyclic hetero Diels-Alder Cycloadducts in good yields. 2. Thiochalcone underwent asymmetric hetero Diels-Alder reactions with some chiral dienophiles to give the cycloadducts with high level of stereoselectivities in excellent yields. The absolute structure was determined. 3. The hetero Diels-Alder reaction of heteroaromatic thioketones with 2-chloroacrylonitrile or 2-haloacrylic esters afforded, after treatment of the cycloadducts with an amine, heterocycle-fused 2H-thiopyran compounds having an ortho-quinodimethane structure. 4. The intermediary thiocarbonyl ylides derived from the reaction of heteroaromatic thioketones with disulfonylcarbene species underwent 1,5-dipolar cyclization with elimination of a sulfinic acid to afford heterocycle-fused [c] thiophenes. 5.1,2-Thiaphospholes, prepared from the reaction of bicyclic trithiophosphates with tributylphosphine, underwent double Diels-Alder reactions with a variety of dienophiles or tandem Diels-Alder reaction/Michael addition reaction to give phosphorus-containing heterocycles. 6. The conjugated carbodiimides preferentially afforded the electrocyclization products under thermal conditions, whereas in the presence of a Lewis acid catalyst they gave the intramolecular Diels-Alder products in a highly periselective manner. 7. Addition reaction of the conjugated carbodiimides with a nucleophile such as an alcohol, an amine and a thiol, followed by intramolecular Michael addition reaction, gave the dihydroquinazoline derivatives.

1. alpha，beta：由2-苯硫基四氢萘衍生的γ，δ-硫代羰基化合物与各种亲二烯体在热或刘易斯酸催化下反应，以良好的产率得到多环杂Diels-Alder环加合物。2.硫代查耳酮与手性亲双烯体发生不对称杂Diels-Alder反应，得到了高立体选择性的环加合物。测定了其绝对结构。3.杂芳族硫酮与2-氯丙烯腈或2-卤代丙烯酸酯的杂Diels-Alder反应，在用胺处理环加合物后，得到具有邻醌二甲烷结构的杂环稠合的2 H-噻喃化合物。4.中间体硫代羰基叶立德衍生自杂芳族硫酮与二磺酰基卡宾物种的反应进行1，5-偶极环化，消除亚磺酸，得到杂环稠合的[c]噻吩。5.1，2-硫代磷杂环化合物由双环三硫代磷酸酯与三丁基膦反应制得，可与多种亲双烯体进行双Diels-Alder反应或串联Diels-Alder反应/Michael加成反应，得到含磷杂环化合物。6.共轭双酰亚胺在热条件下优先得到电环化产物，而在刘易斯酸催化剂的存在下，它们以高周选择性的方式得到分子内的Diels-Alder产物。7.通过共轭二氢喹唑啉酰亚胺与醇、胺、硫醇等亲核试剂的加成反应，再与分子内的Michael加成反应，得到了二氢喹唑啉衍生物。

项目成果

Satoshi Moriyama: "Thermal and Lewis Acid-Promoted Hetero Diels-Alder Reactions of α,β:γ,δ-Unsaturated Carbodithioic Esters and Carbothioic O-Esters;5,6-Dihydro-2H-naphtho[1,2-b]thiopyran-3-carbodithioates and -carbothioic O-Esters" Bull.Chem.Soc.Jpn.67.

Satoshi Moriyama：“热和路易斯酸促进的 α,β:γ,δ-不饱和碳二硫酸酯和硫碳 O-酯的杂狄尔斯-阿尔德反应；5,6-二氢-2H-萘并[1,2-b]噻喃-3-二硫代碳酸酯和-硫代碳酸酯”Bull.Chem.Soc.Jpn.67。

S.Moriyama, T.Karakasa, T.Saito, and S.Motoki: "Kinetic Stability as Monomeric Forms of 2-Alkyl-5,6-dihydro-3-thioacety1-2H-naphtho [1,2-b] thiopyrans" Bull.Chem.Soc.Jpn.66. 2124-2127 (1993)

S.Moriyama、T.Karakasa、T.Saito 和 S.Motoki：“2-烷基-5,6-二氢-3-硫代乙酰基1-2H-萘并[1,2-b]噻喃单体形式的动力学稳定性”

Takao Saito: "A Simple and Efficent Synthesis of Heterocycle-Fused 2H-Thiopyrans,Furo-,Benzofuro-,Thieno-,Benzothieno-,Pyrrolo-,and Indolo-2H-thiopyrans,from Heteroaromatic Thioketones and α-Chloroacrylonitrile or α-Bromacrylic Esters via a Hetero Diels-A

Takao Saito：“由杂芳族硫酮和 α-氯丙烯腈或 α-溴丙烯酸简单高效合成杂环稠合 2H-噻喃、呋喃-、苯并呋喃-、噻吩基-、苯并噻吩基-、吡咯并-和吲哚-2H-噻喃通过异狄尔斯-A 形成酯

T.Saito, S.Gon, H.Kikuchi, and S.Motoki: "Reaction of Aromatic Thioketones with the Carbenoids Generated from Phenyl-iodonium Bis (Phenylsulfonyl) methylide and Bis (arylsulfonyl) diazomethanes : Reinvestigation of the Reaction Involving a Revised Structu

T.Saito、S.Gon、H.Kikuchi 和 S.Motoki：“芳香族硫酮与由苯基碘鎓双（苯基磺酰基）甲基化物和双（芳基磺酰基）重氮甲烷生成的类胡萝卜素的反应：对涉及修订结构的反应的重新研究

T.Saito, T.Shizuta, H.Kikuchi, J.Nakagawa, K.Hirotsu, H.Ohmura, and S.Motoki: "A Simple and Efficent Synthesis of Heterocycle-Fused 2H-Thiopyrans, Furo-, Benzofuro-, Thieno-, Benzothieno-, Pyrrolo-, and Indolo-2H-thiopyrans, from Heteroaromatic Thioketone

T.Saito、T.Shizuta、H.Kikuchi、J.Nakakawa、K.Hirotsu、H.Ohmura 和 S.Motoki：“杂环稠合 2H-噻喃、Furo-、Benzofuro-、Thieno 的简单有效合成