Studies on Remote Asymmetric Induction Using Chiral Pyrrolyl Sulfoxides and its Catalytic Reactions

手性吡咯亚砜远程不对称诱导及其催化反应研究

• 批准号: 11672110
• 负责人: ARAI Yoshitsugu
• 金额: $ 1.47万
• 依托单位: GIFU PHARMACEUTICAL UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11672110/
• 关键词: chiral sulfoxide; Diels-Alder reaction; asymmetric reduction; remote asymmetric induction; α, β-unsaturated ketone; Lewis acid; dienophile; diastereoselective; conjugate addition; ディールス・アルダー反応; ルイス酸

1. Diels-Alder reaction of 2-(p-tolylsulfinyl) pyrrolyl enones {(E)-cinnamoyl, (E)-pent-2-enoyl and crotonoyl} with cyclopentadiene proceeded smoothly to give the corresponding endo adducts as a single isomer (>90% diastereoisomeric excesses) in the presence of a Lewis acid such a lanthanoid triflate and aluminum (III) chloride.2. Conjugate addition reaction to chiral 2-(p-tolylsulfinyl) pyrrolyl (E)-cinnamoyl and crotonoyl ketones using (di) alkyl cuprates afforded the corresponding two addition products with up to 30% diastereoisomeric excesses. On the other hand, addition reactions to chiral 2-(p-tolylsulfinyl) pyrrolyl (E)-cinnamoyl ketones with (di) aryl cuprates such as o-tolyl-, p-tolyl-, and (1-naphthyl)-cuprates afforded the corresponding addition products which have R configuration with >90% diastereoisomeric excesses. Similar reactions to the crotonoyl derivative by arylcuprates afforded the addition products with modest to excellent diastereoselectivities.The absolute stereochemistry at newly formed asymmetric carbon center of the major products was determined by X-ray analysis or by transformation into the known compounds by alcoholysis. In particular for these two addition reactions, the auxiliary (i.e.the sulfinyl pyrrole) was recovered by alcoholysis of the products without any loss of optical purity.

1. 2-（对甲苯亚磺酰基）吡咯基烯酮（E-肉桂酰基、E-己烯酰基和巴豆酰基）与环戊二烯在镧系元素三氟甲磺酸盐和三氯化铝等刘易斯酸存在下，顺利地进行Diels-Alder反应，得到相应的单一异构体的内加成物（非对映异构体过量>90%）.用铜酸（二）烷基酯与手性2-（对甲苯亚磺酰基）吡咯基（E）-肉桂酰基酮和巴豆酰基酮进行共轭加成反应，得到相应的两种加成产物，非对映异构体过量高达30%。另一方面，手性2-（对甲苯亚磺酰基）吡咯基（E）-肉桂酰酮与（二）芳基铜酸酯如邻甲苯基-、对甲苯基-和（1-萘基）-铜酸酯的加成反应得到了相应的加成产物，其R构型的非对映异构体过量>90%。与巴豆酰基衍生物类似的反应得到了具有中等至优异非对映选择性的加成产物，主要产物在新形成的不对称碳中心的绝对立体化学通过X-射线分析或通过醇解转化为已知化合物来确定。特别是对于这两个加成反应，助剂（即亚磺酰基吡咯）通过产物的醇解回收，而没有任何光学纯度的损失。

项目成果

Y.Arai: "Remote Asymmetric Induction Using Chiral(p-Tolylsulfinyl)-furyl,-thienyl and -pyrroryl carbonyl Compounds"Reviews on Heteroatom Chem.. 21. 65-91 (2000)

Y.Arai：“使用手性(对甲苯亚磺酰基)-呋喃基、-噻吩基和-吡咯基羰基化合物进行远程不对称感应”杂原子化学评论. 21. 65-91 (2000)

Y.Arai et al.: "1,6-Asymmetric Induction during the Conjugate Addition of Arylcopper Reagents to Chiral Sulfinyl-Substituted pyrrolyl α,β-Unsaturated Enones"Synlett. xxxx-xxxx (2001)

Y.Arai 等人：“芳基铜试剂与手性亚磺酰基取代的吡咯基 α,β-不饱和烯酮共轭加成过程中的 1,6-不对称诱导”Synlett。

Y.Arai et al.: "Recoverable chiral sulfoxide : remote asymmetric induction in Lewis acid-promoted Diels-Alder reaction of chiral sulfinyl substituted pyrrolyl α, β-unsaturated enones"J.Chem.Soc., Perkin Trans. 1. 2165-2170 (1999)

Y.Arai 等人：“可回收的手性亚砜：手性亚磺酰基取代的吡咯基 α, β-不饱和烯酮的路易斯酸促进的 Diels-Alder 反应中的远程不对称诱导”J.Chem.Soc.，Perkin Trans. 1. 2165- 2170 (1999)

Y.Arai et al.: "Asymmetric Synthesis of (+)-Dihydrokawain-5-ol"J.Org.Chem.. 65. 258-262 (2000)

Y.Arai 等：“( )-二氢卡因-5-醇的不对称合成”J.Org.Chem.. 65. 258-262 (2000)

Y.Arai et al.: "Remote asymmetric induction using chiral (p-tolylsulfinyl)-furyl, -thienyl and -pyrrolyl carbonyl compounds"Rev.Heteroatom Chem.. 21. 65-91 (1999)

Y.Arai 等人：“使用手性（对甲苯亚磺酰基）-呋喃基、-噻吩基和-吡咯基羰基化合物进行远程不对称诱导”Rev.Heteroatom Chem.. 21. 65-91 (1999)