铱催化的手性 β-立体醇的烯丙基化反应：绕过可外消旋化的醛的离散形成。
Iridium-catalyzed allylation of chiral β-stereogenic alcohols: bypassing discrete formation of epimerizable aldehydes.
机构信息
University of Texas at Austin, Department of Chemistry and Biochemistry, Austin, Texas 78712, United States.
出版信息
Org Lett. 2012 Dec 21;14(24):6302-5. doi: 10.1021/ol3030692. Epub 2012 Dec 11.
Abstract
The cyclometalated π-allyliridium 3,4-dinitro-C,O-benzoate complex modified by (R)- or (S)-Cl,MeO-BIPHEP promotes the transfer hydrogenative coupling of allyl acetate to β-stereogenic alcohols with good to excellent levels of catalyst-directed diastereoselectivity to furnish homoallylic alcohols. Remote electronic effects of the C,O-benzoate of the catalyst play a critical role in suppressing epimerization of the transient α-stereogenic aldehyde.
摘要
（R）-或（S）-Cl，MeO-BIPHEP 修饰的环金属化π-烯丙基铱 3,4-二硝基-C,O-苯甲酸盐配合物促进烯丙基乙酸酯与β-手性醇的转移氢化偶联，以高至优秀的催化剂导向非对映选择性得到高烯丙醇。催化剂的 C,O-苯甲酸盐的远程电子效应在抑制瞬态α-手性醛的差向异构化中起着关键作用。
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1
2
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3
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Chem Rev. 2011 Dec 14;111(12):7774-854. doi: 10.1021/cr1004474. Epub 2011 Sep 16.
4
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Top Organomet Chem. 2011 Jan 1;34(2011):107-138. doi: 10.1007/978-3-642-15334-1_5.
5
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Org Lett. 2011 Aug 5;13(15):4036-9. doi: 10.1021/ol201547q. Epub 2011 Jul 11.
6
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Org Lett. 2011 May 6;13(9):2488-91. doi: 10.1021/ol2007378. Epub 2011 Apr 4.
7
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