Use of group 4 bis(sulfonamido) complexes in the intramolecular hydroamination of alkynes and allenes.
Use of group 4 bis(sulfonamido) complexes in the intramolecular hydroamination of alkynes and allenes.
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DOI：
10.1021/ja0361547
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发表时间：
2003-09
影响因子：
15
通讯作者：
L. Ackermann;R. Bergman;Rebecca N. Loy
中科院分区：
文献类型：
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作者：
L. Ackermann;R. Bergman;Rebecca N. Loy
四钛(氨基)络合物对烯烃和烯烃的分子内氢胺化反应的催化效率比基于CP的物种更高。在这里，我们报告了双(磺酰胺)配体的电子吸引和空间要求导致了催化活性的提高。还制备了锆类似物，并对对甲苯磺基取代的配合物20进行了结构表征。与钛系列催化剂一样，双(磺酰胺基)锆催化剂比双(环戊二烯基)配合物Cp(2)ZrMe(2)(23)更有效地催化烯烃的分子内氢胺化反应。此外，这些化合物还可以将具有高立体选择性的1，3-二取代氨基烯转化为Z-烯丙胺，并允许三取代联烯的氢胺化反应。合成了双(磺酰胺基)亚胺钛配合物27。它以与四(酰胺)15相当的速度将氨基烯10转化为环亚胺11，支持了催化活性钛亚胺中间体的假说。
Titanium tetrakis(amido) complexes catalyze the intramolecular hydroamination of alkynes and allenes more efficiently than Cp-based species. We report here that electron-withdrawing and sterically demanding bis(sulfonamido) ligands lead to enhanced catalytic activity. Zirconium analogues have also been prepared, and the tosyl-substituted complex 20 has been structurally characterized. As in the titanium series, bis(sulfonamido) zirconium catalysts are more efficient in the intramolecular hydroamination of allenes than bis(cyclopentadienyl) complex Cp(2)ZrMe(2) (23). Furthermore, these compounds transform 1,3-disubstituted aminoallenes with high stereoselectivity to the Z-allylamines and allow the hydroamination of a trisubstituted allene. Titanium bis(sulfonamido) imido complex 27 was synthesized. It converts aminoallene 10 to cylic imine 11 with a rate comparable to that of tetrakis(amide) 15, supporting the hypothesis of a catalytically active titanium imido intermediate.