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

复古-α，α-二异丙基高烯丙醇与氯化锡和N-氯代丁二酰亚胺在二氯甲烷中于-40℃进行羰基烯丙基化反应，得到烯丙基三氯锡，并将其用于羰基烯丙基化和亚胺烯丙基化反应。导致与各种醛的亲核加成，以高产率产生1-取代的3-丁烯-1-醇。由α，α-二异丙基-β-甲基高烯丙醇衍生的2-丁烯基三氯锡与不带配位基团或带非配位吸电子基团的醛的亲核加成反应具有α-区域选择性，与通常的2-丁烯基金属试剂相反。2）亚胺烯丙基化2-丙烯基三氯锡与由醛和甲苯磺酰胺衍生的N-甲苯磺酰亚胺和氯化锡（II）及NCS发生亲核加成反应，以高产率制备1-取代的N-甲苯磺酰基-3-丁烯基胺。2-丁烯基三氯锡不能用于N-甲苯磺酰亚胺的亲核加成反应。N-对甲苯磺酰亚胺能与烯丙基三氯锡形成六元环过渡态，用它代替N-对甲苯磺酰亚胺与2-丙烯基三氯锡和2-丁烯基三氯锡反应，以较好的产率得到相应的高烯丙基胺。

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.