Ligand-controlled access to [4 + 2] and [4 + 3] cycloadditions in gold-catalyzed reactions of allene-dienes.

Ligand-controlled access to [4 + 2] and [4 + 3] cycloadditions in gold-catalyzed reactions of allene-dienes.
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DOI:
10.1021/ja901649s
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发表时间:
2009-05-13
影响因子:
15
通讯作者:
Toste FD
Toste FD
中科院分区:
化学1区
文献类型:
--
作者:
Mauleón P;Zeldin RM;González AZ;Toste FD

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通过调节辅助配体的电子性质,可以实现金(I)催化的二烯-联烯的[4+2]-或[4+3]-环加成反应的高选择性。三芳基亚磷酰金(I)配合物用作α [4+2]-环加成反应的催化剂,该反应导致亚烷基环己烯。相反,二叔丁基联苯膦金(I)催化的反应通过[4+3]-环加成反应得到环庚二烯。
By adjusting the electronic properties of the ancilliary ligands high selectivity can be achieved for either gold(I)-catalyzed [4+2]- or [4+3]-cycloaddition reactions of diene-allenes. Triarylphosphitegold(I) complexes are employed as catalysts for a [4+2]-cycloaddition reactions leading to alkylidenecyclohexenes. Conversely, di-t-butylbiphenylphosphinegold(I)-catalyzed reactions afford cycloheptadienes via [4+3]-cycloaddition reactions.
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