Enantioselective Divergent Synthesis of (-)-cis-alpha- and (-)-cis-gamma-irone by Using Wilkinson's Catalyst

Bugoni Serena; Boccato Debora; Porta Alessio; Zanoni Giuseppe; Vidari Giovanni

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Enantioselective Divergent Synthesis of (-)-cis-alpha- and (-)-cis-gamma-irone by Using Wilkinson's Catalyst

机译：用威尔金森催化剂对映体选择性合成（-）-顺式-α-和（-）-顺式-γ-酮

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A simple, efficient synthesis is reported for (-)-cis-alpha- and (-)-cis-gamma-irone, two precious constituents of iris oils, in >= 99% diastereomeric and enantioselective ratios. The two routes diverge from a common intermediate prepared from (-)-epoxygeraniol. Of general interest in this approach is the installation of the enone moiety of irones through a NHC Au'-catalyzed Meyer Schuster-like rearrangement of a propargylic benzoate and the use of Wilkinson's catalyst for the stereoselective hydrogenation of a prostereogenic exocyclic double bond to secure the critical cis stereochem- istry of the alkyl groups at C2 and C6 of the irones. The stereochemical aspects of this reaction are rationally supported by DFT calculation of the conformers of the substrates undergoing the hydrogenation and by a modeling study of the geometry of the rhodium eta(2) complexes involved in the diastereodifferentiation of the double bond faces. Thus, computational investigation of the eta(2) intermediates formed in the catalytic cycle of prostereogenic alkene hydrogenation by using Wilkinson's catalyst could be highly predictive of the stereochemistry of the products.

机译：据报道，鸢尾油的两种珍贵成分（-）-顺式-α-和（-）-顺式-γ-酮的简单，高效合成方法，其非对映异构体和对映体选择性比率≥99％。两种途径与由（-）-环氧香叶醇制备的普通中间体不同。在这种方法中，人们普遍感兴趣的是通过NHC Au'催化的炔丙基苯甲酸酯的Meyer Schuster样重排来安装铁的烯酮部分，并使用Wilkinson的催化剂进行立体生成的环外双键的立体选择性加氢以确保熨烫物C2和C6处的烷基的关键顺式立体化学。 DFT计算进行氢化的底物的构象异构体，并通过对涉及双键面非对映分化的铑eta（2）配合物的几何形状的建模研究，合理地支持了该反应的立体化学方面。因此，使用威尔金森催化剂对在酯基烯烃加氢催化循环中形成的eta（2）中间体的计算研究可高度预测产物的立体化学。

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《Chemistry: A European journal》 |2015年第2期|共9页
作者
Bugoni Serena; Boccato Debora; Porta Alessio; Zanoni Giuseppe; Vidari Giovanni;
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fragramces; hydrogenation; terpenoids; total synthesis; wilkinson's catalyst;

机译：碎片;加氢;萜类化合物;全合成;威尔金森催化剂;

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1. Enantioselective Divergent Synthesis of (-)-cis-alpha- and (-)-cis-gamma-irone by Using Wilkinson's Catalyst [J] . Bugoni Serena, Boccato Debora, Porta Alessio, Chemistry: A European journal . 2015,第2期

机译：用威尔金森催化剂对映体选择性合成（-）-顺式-α-和（-）-顺式-γ-酮
2. Enantioselective catalysis; 123: Octaaldehyde type chelating ligands - A divergent synthesis approach to easily tunable expanded ligands for enantioselective catalysis [J] . Brunner H., Stefaniak S., Janura M. Synthesis: International Journal of Methods in Synthetic Organic Chemistry . 1998,第12期

机译：对映选择性催化; 123：八醛型螯合配体-一种易于调节的扩展配体用于对映体选择性催化的发散合成方法
3. CATALYTIC ENANTIOSELECTIVE REACTIONS .7. SYNTHESIS OF NEW BETA-AMINOALCOHOLS DERIVED FROM ALPHA-D-GLUCOSE AS CHIRAL CATALYSTS FOR THE CATALYTIC ENANTIOSELECTIVE ADDITION OF DIETHYLZINC TO ALDEHYDES [J] . Cho BT., Kim N. Synthetic Communications . 1996,第5期

机译：催化对映选择性反应.7。合成α-D-葡萄糖为手性催化剂的新型β-氨基醇，用于二乙锌向醛的催化对映选择性加成
4. Synthesis of 4,4'-Biquinazoline alcohols as Chiral catalysts in Enantioselective Alkynation of Aldehydes with Phenylacetylene [C] . Hamdullah Kilic, Mustafa Catir, Murat Cakici European Symposium on Organic Chemistry . 2009

机译：用苯乙炔合成4,4'-比喹唑啉醇作为对酰醛酰醛醇醇的手性催化剂
5. Part I. Asymmetric organocatalysis: (1) Direct enantioselective organocatalytic hydroxymethylation of aldehydes catalyzed by alpha,alpha-diphenylprolinol trimethylsilyl ether: Application in the formal synthesis of (-)-Rasfonin; (2) Synthesis of a novel bicyclic secondary amine organocatalyst: Application to the direct enantioselective organocatalytic hydroxymethylation of aldehydes. Part II. Asymmetric synthesis of bicyclic analogues of the anti-osteoporotic drug risedronate. [D] . Miller, John Robert. 2010

机译：第一部分，不对称有机催化：（1）α，α-二苯基脯氨醇三甲基甲硅烷基醚催化的醛的直接对映选择性有机催化羟甲基化：在（-）-Rasfonin的正式合成中的应用；（2）新型双环仲胺有机催化剂的合成：应用于醛的直接对映选择性有机催化羟甲基化。第二部分抗骨质疏松药物Risedronate的双环类似物的不对称合成。
6. Design and Stereoselective Preparation of a New Class of Chiral Olefin Metathesis Catalysts and Application to Enantioselective Synthesis of Quebrachamine: Catalyst Development Inspired by Natural Product Synthesis [O] . Elizabeth S. Sattely, Simon J. Meek, Steven J. Malcolmson, -1

机译：新型手性烯烃复分解催化剂的设计和立体选择性制备及其在Quebrachamine对映选择性合成中的应用：天然产物合成的启发
7. Design and Stereoselective Preparation of a New Class of Chiral Olefin Metathesis Catalysts and Application to Enantioselective Synthesis of Quebrachamine: Catalyst Development Inspired by Natural Product Synthesis [O] . Elizabeth S. Sattely, Simon J. Meek, Steven J. Malcolmson, 2008

机译：设计和立体选择性制备新一类手性烯烃复分解催化剂及其对Quebrachamine的映射合成的应用：催化剂发展灵感来自天然产物合成

Enantioselective Divergent Synthesis of (-)-cis-alpha- and (-)-cis-gamma-irone by Using Wilkinson's Catalyst

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