Asymmetric Cycloaddition Using Coordination Ability of Heteroatom with Organometallics

利用杂原子与有机金属配位能力的不对称环加成反应

• 批准号: 05671744
• 负责人: ARAI Yoshitsugu
• 金额: $ 1.15万
• 依托单位: Gifu Pharmaceutical 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: 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-05671744/
• 关键词: Heteroatom; Sulfide; Sulfoxide; Diethlzinc; Diastereoselectivity; Allylmetal; Furan; Thiophen; スルフイド; 不斉付加反応; ヘテロ原子リガンド; 有機金属

Heteroatoms in organic chemistry have become a powerful tool for asymmetric synthesis as a chiral ligand with organometals. We focused on the sulfur atom, incorporated a chiral molecule, which could coordinate with organometals. The aim of this resaerch project is thus to develope an addition reaction of such organometalic compounds as diethylzinc to an aldehyde in the presence of chiral camphor-derived ligands containing the sulfur as sulfides or sulfoxides. Furthermore, the effectiveness of a sulfinyl group in the beta-sulfinyl carbonyl compounds, as chiral auxiliary, which may form a seven-membered chelate with a Lewis acid in the allylation by allylmetal compounds.1. We synthesized some, camphor-derived sulfides and sulfoxides and selected the enantioselective addition of bezaldehyde with diethylzinc. When benzaldhyde was reacted with diethylzinc using beta-oxysulfides, (S) -1-phenyl -1-propanol was obtained in up to 82%e.e.under the optimized conditions.2.We undertook the asymmetric addition of an allylmetal compound to chiral beta-sulfinyl aldehyde in the presence of a Lewis acid. Despite of numerous reports for asymmetric condensations using alpha-sulfinyl carbonyl compounds, little work has been done on the asymmetric addition to beta-sulfinyl carbonyl compounds because of its low performance in chelation control. We thus synthesized chiral beta-sulfinyl carbonyl compounds i.e., chiral p-tolylsulfinyl fyrylaldehydes and examined the diastereoselective addition reactions. The addition of allyltriphenylstannane to 3-sulfinylfurfural in the presence of titanium (IV) tetrachloride proceeded with high diastereoselectivity to give the homoallyl alcohol. On the other hand the similar treatment of the sufinyl aldehyde with tin (IV) tetrachloride afforded the other diastereoisomeric alcohol, exclusively.The similar results were also obtained in the case of chiral, sulfinyl-substituted thienyl aldehyde.

杂原子作为有机金属化合物的手性配体，在有机化学中已成为不对称合成的有力工具。我们将重点放在硫原子上，引入一个手性分子，它可以与有机金属配位。因此，本研究项目的目的是开发在含硫的硫化物或亚砜的手性衍生物衍生的配体存在下，诸如二乙基锌的有机化合物与醛的加成反应。此外，β-亚磺酰基羰基化合物中的亚磺酰基作为手性助剂，在烯丙基金属化合物的烯丙基化反应中，可与刘易斯酸形成七元螯合物.本文合成了几种含硫醚和亚砜，并选择了苯甲醛与二乙基锌的不对称加成反应。在优化的反应条件下，苯甲醛与二乙基锌通过β-硫氧化物反应，得到了（S）-1-苯基-1-丙醇，收率可达82% e.e.。2.在刘易斯酸存在下，进行了烯丙基金属化合物与手性β-亚磺醛的不对称加成反应。尽管使用α-亚磺酰基羰基化合物进行不对称缩合的报道很多，但对β-亚磺酰基羰基化合物的不对称加成的工作很少，因为其在螯合控制中的低性能。因此，我们合成了手性β-亚硫酰基羰基化合物，即，手性对甲苯基亚磺酰基苯甲醛并检查了非对映选择性加成反应。在四氯化钛存在下，烯丙基三苯基锡烷与3-亚磺酰基糠醛的加成反应以高的非对映选择性进行，得到高烯丙醇。另一方面，用四氯化锡（IV）对亚磺酰基醛进行类似的处理，只得到了另一种非对映异构体醇，在手性亚磺酰基取代的噻吩基醛的情况下也得到了类似的结果。

项目成果

Y.Arai, M.Matsu, A.Fujii, T.Kontani, T.Ohno, T.Koizumi, M.Shiro: ""Diels-Alder Reactions of Optically Active alpha- (2-exo-Hydroxy-10-bornylsulfinyl) maleimides and its Application to Optically Active 5-Functionalised Pyrrolines via Retro-Diels-Alder Reac

Y.Arai、M.Matsu、A.Fujii、T.Kontani、T.Ohno、T.Koizumi、M.Shiro：“光学活性 α-（2-exo-Hydroxy-10-bornylsulfinyl）的 Diels-Alder 反应

Y.Arai: ""Asymmetric Diels-Alder Reactions Using Chiral alpha, beta-Unsaturated Sulfoxides as Efficient Dienophiles."" Ann.Proc.Gifu Pharm.Univ.44. (1995)

Y.Arai：“使用手性 α、β-不饱和亚砜作为高效亲双烯体的不对称 Diels-Alder 反应。”Ann.Proc.Gifu Pharm.Univ.44。

Y.Arai: "光学活性α,β-不飽和スルホキシドを用いる不斉デイールス・アルダー反応と天然物合成への応用" 薬学雑誌. 114. 201-218 (1994)

Y.Arai：“使用光学活性 α,β-不饱和亚砜的不对称 Diels-Alder 反应及其在天然产物合成中的应用”Pharmaceutical Journal 114. 201-218 (1994)。

T.Takahashi, N.Kurose, S.Kawanami, Y.Arai, T Koizumi, M.Shiro: ""Optically Pure Haloselenuranes.First Synthesis and Nucleophilic Substitutions."" J.Org.Chem.59. 3262-3264 (1994)

T.Takahashi、N.Kurose、S.Kawanami、Y.Arai、T Koizumi、M.Shiro：“光学纯卤代烷。首次合成和亲核取代。”J.Org.Chem.59。

Y.Arai et al.: "Enantioselective Synthesis of (+)-Indolizidine,(+)-Laburnine and (+)-Elaeokanines A and C Using the Diels-Alder Reactions of α-(2-exo-Hydroxy-10-bornylsulfinyl)maleimides" J.Chem.Soc.,Perkin Trans.1. 15-24 (1994)

Y.Arai 等人：“使用 α-(2-exo-Hydroxy-10-bornylsulfinyl) 的 Diels-Alder 反应对映选择性合成 (+)-Indolizidine、(+)-Laburnine 和 (+)-Elaeokanines A 和 C )马来酰亚胺”J.Chem.Soc.，Perkin Trans.1. 15-24 (1994)