A Novel Preparation of Allylic Tins from α,α-Disubstituted Homoallylic Alcohols and Its Application

α,α-二取代高烯丙醇制备烯丙基锡的新方法及其应用

• 批准号: 12640573
• 负责人: MASUYAMA Yoshiro
• 金额: $ 1.98万
• 依托单位: Sophia University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640573/
• 关键词: Carbonyl-allylation; Allylic trichlorotins; Homoallylic alcohols; Tin(II) chloride; N-Chlorosuccinimide; Imine-allylation; Retro-allylation; Regioselectivity; N-トシルイミニウム

The retro-(carbonyl-allylation) of α, α-diisopropylhomoallylic alcohols with tin(1I) chloride and N-chlorosuccinimide (NCS) in dichioromethane at -40℃ affords allylic trichiorotins that are utilized for carbonyl-allylation and imine-allylation.1) Carbonyl-allylation2-Propenyltrichlorotin, derived from α, α-diisopropylhomoallyl alcohol, causes nucleophilic addition to various aldehydes to produce 1-substituted 3-buten-1-ols in high yields. The nucleophilic addition of 2-butenyltrichlorotin, derived from α, α-diisopropyl-β-methylhomoallyl alcohol, to aldehydes, bearing no coordinating groups or bearing non-coordinating electron-withdrawing groups, exhibits cc-regioselectivity, in contrast to that of usual 2-butenylmetal reagents.2) Imine-allylationThe 2-propenyltrichlorotin causes nucleophilic addition to N-tosyliminiums, derived from aldehydes and tosylamide with tin(II) chloride and NCS, to produce 1-substituted N-tosyl-3-butenylamines in good yields. The 2-butenyltrichlorotin cannot be applied to the nucleophilic addition to N-tosyliminiums. N-Tosylimines, which can form six-membered cyclic transition state with allylic trichiorotins, instead of using N-tosyliminiums react with not only 2-propenyltrichiorotin but also 2-butenyltrichiorotin to afford the corresponding homoallylic amines in good yields.

α， α-二异丙基同丙烯醇与氯化锡和n -氯琥珀酰亚胺在二氯甲烷中-40℃还原羰基烯丙基化反应，得到用于羰基烯丙基化和亚胺烯丙基化反应的烯丙基三基蛋白。1)由α， α-二异丙基均烯丙醇衍生的羰基烯丙基- 2-丙烯三氯丁酮，可与各种醛发生亲核加成反应，产率高，得到1-取代的3-丁醇。由α， α-二异丙基-β-甲基同丙烯醇衍生的2-丁基三氯锡与不含配位基团或不含配位吸电子基团的醛的亲核加成，与通常的2-丁基金属试剂相比，表现出cc-区域选择性。2)亚胺烯丙基：2-丙烯基三氯锡与氯化锡（II）和NCS由醛和甲苯酰胺衍生而来的n -甲苯胺发生亲核加成反应，产率较高，可得到1取代的n -甲苯-3-丁烯胺。2-丁基三氯不能应用于n -苯三胺的亲核加成。N-Tosylimines可以与烯丙基三氟氰胺形成六元环过渡态，可以代替n - tosyliums与2-丙烯基三氟氰胺和2-丁烯基三氟氰胺反应，产率高。

项目成果

Yoshiro Masuyama: "A Novel Preparation of Allylic Trichlorotins from α, α-Diisopropyl-homoallylic Alcohols and Its Application to Carbonyl Allylations"Synlett. 11. 1802-1804 (2001)

Yoshiro Masuyama：“从 α, α-二异丙基高烯丙醇制备烯丙基三氯锡及其在羰基烯丙基化中的应用”Synlett。11. 1802-1804 (2001)

Yoshiro Masuyama: "A Novel Preparation ofAllylic Trichlorotins from a, oc-Diisopropylhomoallylic Alcohols and Its Application to Carbonyl Allylations"Synlett. 11. 1802-1804 (2001)

Yoshiro Masuyama：“从α，α-二异丙基高烯丙醇中制备烯丙基三氯锡及其在羰基烯丙基化中的应用”Synlett。

Yoshiro Masuyama: "A Novel Preparation of Allylic Trichlorotins from α,α-Diisopropyl-homoallylic Alcohols and Its Application to Carbonyl Allations"Synlett. 1802-1804 (2001)

Yoshiro Masuyama：“从 α,α-二异丙基高烯丙醇制备烯丙基三氯锡及其在羰基化中的应用”Synlett 1802-1804 (2001)。