BF3.cntdot.Et2O-Promoted Allylation Reactions of Allyl(cyclopentadienyl)iron(II) Dicarbonyl Complexes with Carbonyl Compounds
BF3.cntdot.Et2O-Promoted Allylation Reactions of Allyl(cyclopentadienyl)iron(II) Dicarbonyl Complexes with Carbonyl Compounds
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BF3.cntdot.Et2O 促进烯丙基(环戊二烯基)铁(II)二羰基配合物与羰基化合物的烯丙基化反应
DOI：
10.1021/om00010a037
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发表时间：
1995
期刊：
影响因子：
2.8
通讯作者：
E. Turos
中科院分区：
文献类型：
--
作者：
Songchun Jiang;G. Agoston;Ti Chen;M. Cabal;E. Turos
研究了路易斯酸促进的烯丙基二羰基铁配合物与醛、酮、亚胺和缩醛的反应。这些添加在温和条件下使用BFa-EtaO进行，得到呈可分离的黄色沉淀的两性离子铁-烯烃络合物。衍生自甲醛的加合物的结构已被其特征在于充分的质子，碳，氟NMR光谱，红外光谱，和快原子轰击（FAB）质谱。用CH 3CN或NaI在丙酮中处理这些铁-烯烃盐，分别得到脱金属的高烯丙醇、胺或醚。3-取代烯丙基铁配合物与醛的加成有利于1，2-顺式加成物的形成，而与起始试剂的E或Z几何构型无关。因此，这些烯丙基化的非对映选择性类似于其他烯丙基金属试剂（烯丙基硅烷，烯丙基锡烷），其添加被假定通过开放（扩展）过渡态进行。
The Lewis-acid-promoted reaction of allyl (cyclopentadienyl) iron dicarbonyl complexes with aldehydes, ketones, imines, and acetals has been investigated. These additions take place under mild conditions using BFa-EtaO to afford zwitterionic iron-alkene-complexes as isolable yellow precipitates. The structures of the-adducts derived fromaldehydes have been characterized fully by proton, carbon, and fluorine NMR spectroscopy, infrared spectroscopy, and fast atom bombardment (FAB) mass spectrometry. Treatment of these iron—olefin salts with CHgCN or Nal in acetone gives the demetalated homoallylic alcohols, amines, or ethers, respectively. The additions of 3-substituted allyliron complexes to aldehydes favor the formation of the 1, 2-syn adduct regardless of the E or Z geometry of the starting reagent. Thus, the diastereofacial selectivityfor these allylations is analogous to that of other allylmetal reagents (allylsilanes, allylstannanes) whose additions have been postulated to proceed through an open (extended) transition state.