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Intramolecular Alkene Hydroamination with Hybrid Catalysts Consisting of a Metal Salt and a Neutral Organic Base
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-08-14 , DOI: 10.1002/ejic.202000671 Philipp C. Stegner 1 , Christian A. Fischer 1 , D. Thao Nguyen 1 , Andreas Rösch 1 , Johanne Penafiel 1 , Jens Langer 1 , Michael Wiesinger 1 , Sjoerd Harder 2
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-08-14 , DOI: 10.1002/ejic.202000671 Philipp C. Stegner 1 , Christian A. Fischer 1 , D. Thao Nguyen 1 , Andreas Rösch 1 , Johanne Penafiel 1 , Jens Langer 1 , Michael Wiesinger 1 , Sjoerd Harder 2
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Hybrid catalysts consisting of alkaline earth iodides (AeI2) and the Schwesinger base tBuP4 catalyse the intramolecular alkene hydroamination of H2C=CHCH2CR2CH2NH2 [CR2=CPh2, C(CH2)5, CMe2]. Activities decrease along the row: Ca > Sr >> Mg > Ba. Hybrid catalysts consisting of tBuP4 and ZnI2, AlI3, FeCI3 or NaI were found to be fully inactive. Also, the hybrid catalyst tBuP3/CaI2 was not active which means that the base strength of the non‐nucleophilic organic base must be higher than that of tBuP3 (pKa BH+ = 38.6). Combinations of tBuP4 with CaX2 (X = Cl, Br, OiPr, OTf, NTf2) were found to be fully inactive which may in part be explained by poor solubility. The hybrid catalysis method is therefore limited to the combination tBuP4/CaI2 but the iodide ligands may be partially or fully replaced by chiral ligands. Chiral modifications of the hybrid catalysts gave in intramolecular alkene hydroamination ee values up to 33 %.
中文翻译：
含金属盐和中性有机碱的杂化催化剂分子内烯烃加氢胺化
由碱土金属碘化物（AeI 2）和Schwesinger碱t Bu P4组成的杂化催化剂催化H 2 C = CHCH 2 CR 2 CH 2 NH 2 [CR 2 = CPh 2，C（CH 2）5， CMe 2 ]。活性沿行减少：Ca> Sr >> Mg> Ba。发现由t Bu P4和ZnI 2，AlI 3，FeCl 3或NaI组成的杂化催化剂是完全惰性的。另外，杂化催化剂t BuP3 / CaI 2没有活性，这意味着非亲核有机碱的碱基强度必须高于t Bu P3的碱基强度（p K a BH + = 38.6）。发现t Bu P4与CaX 2（X = Cl，Br，O i Pr，OTf，NTf 2）的组合是完全无活性的，这部分可以由溶解性差解释。因此，混合催化方法仅限于t Bu P4 / CaI 2的组合但是碘化物配体可以被手性配体部分或完全代替。杂化催化剂的手性改性使分子内烯烃加氢胺ee值高达33％。
更新日期：2020-09-15
中文翻译：
含金属盐和中性有机碱的杂化催化剂分子内烯烃加氢胺化
由碱土金属碘化物（AeI 2）和Schwesinger碱t Bu P4组成的杂化催化剂催化H 2 C = CHCH 2 CR 2 CH 2 NH 2 [CR 2 = CPh 2，C（CH 2）5， CMe 2 ]。活性沿行减少：Ca> Sr >> Mg> Ba。发现由t Bu P4和ZnI 2，AlI 3，FeCl 3或NaI组成的杂化催化剂是完全惰性的。另外，杂化催化剂t BuP3 / CaI 2没有活性，这意味着非亲核有机碱的碱基强度必须高于t Bu P3的碱基强度（p K a BH + = 38.6）。发现t Bu P4与CaX 2（X = Cl，Br，O i Pr，OTf，NTf 2）的组合是完全无活性的，这部分可以由溶解性差解释。因此，混合催化方法仅限于t Bu P4 / CaI 2的组合但是碘化物配体可以被手性配体部分或完全代替。杂化催化剂的手性改性使分子内烯烃加氢胺ee值高达33％。
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