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首页> 外文期刊>Organometallics >Synthesis of optically pure o-formylcyclopentadienyl metal complexes of 17 alpha-ethynylestradiol. Recognition of the planar chirality by the estrogen receptor
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Synthesis of optically pure o-formylcyclopentadienyl metal complexes of 17 alpha-ethynylestradiol. Recognition of the planar chirality by the estrogen receptor

机译：17α-乙炔基雌二醇的光学纯o-甲酰基环戊二烯基金属配合物的合成。雌激素受体对平面手性的识别

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A formyl group has been introduced onto the cyclopentadienyl ring of 17 alpha-ethynylestradiol derivatives bearing a ferrocenyl, a cymantrenyl, or a cyrhetrenyl group at the ortho position with respect to the ethynyl group. The presence of this group on the cyclopentadienyl ring induces a planar chirality that provokes the formation of two diastereomers, the Sp and Rp derivatives. These compounds were prepared from Sp and Rp 1-formyl-2-iodoferrocenes, -cymantrenes, and -cyrhetrenes, which were separately prepared by using a combination of suitable ortho directing substituents, such as methoxymethyldioxane and p-tolylsulfoxide, as well as trimethylsilyl as a temporary blocking group. A cross-coupling reaction between these precursors and 17 alpha-ethynylestradiol led to the formation of the hormone complexes. The ferrocenyl hormone compounds were only obtained from a Sonogashira reaction, the cyrhetrenyl compounds were only formed by using a Stille reaction, and the cymantrenyl compounds were obtained from both reactions. A tentative explanation for this interesting behavior is proposed. The affinity of the R diastereomers for the R receptor of estradiol is almost twice that of the S diastereomers. This is the first example of estradiol receptor discrimination between organometallic diastereomers possessing planar chirality. However, in contrast to 1,2-disubstituted derivatives, when the formyl group is at the 1,3-position, the receptor does not differentiate between the two planar chiral diastereomers.
机译：甲酰基已被引入到17个α-乙炔基雌二醇衍生物的环戊二烯基环上，该衍生物在相对于乙炔基的邻位带有二茂铁基，cymantrenyl或cyyrhetrenyl。该基团在环戊二烯基环上的存在诱导了平面手性，该手性引发了两个非对映异构体Sp和Rp衍生物的形成。这些化合物由Sp和Rp 1-甲酰基-2-碘二茂铁，-cymantrenes和-cyrhetrenes制备，它们分别通过结合使用合适的邻位取代基如甲氧基甲基二恶烷和对甲苯基亚砜以及三甲基甲硅烷基制备。临时阻止组。这些前体与17α-乙炔基雌二醇之间的交叉偶联反应导致了激素复合物的形成。二茂铁基激素化合物仅通过Sonogashira反应获得，Cyrhetrenyl基化合物仅通过使用Stille反应形成，而cymantrenyl基化合物则从两个反应中获得。提出了对此有趣行为的初步解释。 R非对映异构体对雌二醇的R受体的亲和力几乎是S非对映异构体的亲和力的两倍。这是具有平面手性的有机金属非对映异构体之间雌二醇受体区分的第一个例子。然而，与1,2-二取代的衍生物相反，当甲酰基位于1,3-位时，受体在两种平面手性非对映异构体之间没有区别。

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