通过钯催化脱氢硼化反应，从环氧化物与二-[B(pin)]-甲烷合成烯基硼酸酯。
Synthesis of Alkenyl Boronates from Epoxides with Di-[B(pin)]-methane via Pd-Catalyzed Dehydroboration.
机构信息
Department of Chemistry, The University of North Carolina , Chapel Hill, North Carolina 27599-3290, United States.
出版信息
Org Lett. 2018 Jan 19;20(2):469-472. doi: 10.1021/acs.orglett.7b03853. Epub 2018 Jan 10.
Abstract
A practical and broadly applicable catalytic method for the synthesis of (E)-alkenylborons is presented. Reactions are promoted by [Pd(Cl)(η-CH)] and proceed by the dehydroboration of cyclic borates. Through the use of epoxides and readily available di-B(pin)-methane (pin = pinacolato), a range of allylic alcohol-containing alkenyl boronates, including those that contain a tertiary alcohol, may be prepared in up to 75% yield and >20:1 E/Z.
摘要
本文提出了一种实用且广泛适用的（E）-烯基硼的催化合成方法。反应由[Pd(Cl)(η-CH)]促进，并通过环状硼酸酯的脱氢硼化进行。通过使用环氧化物和易得的双-B(pin)-甲烷（pin = 频哪醇基），可以制备一系列含有烯丙醇的烯基硼酸酯，包括那些含有叔醇的化合物，收率高达 75%，E/Z 比大于 20:1。
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1
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2
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Org Lett. 2017 Jul 7;19(13):3498-3501. doi: 10.1021/acs.orglett.7b01474. Epub 2017 Jun 13.
3
Amide α,β-Dehydrogenation Using Allyl-Palladium Catalysis and a Hindered Monodentate Anilide.使用烯丙基钯催化和位阻单齿酰胺的酰胺 α，β-脱氢反应。
J Am Chem Soc. 2016 Feb 3;138(4):1166-9. doi: 10.1021/jacs.5b12924. Epub 2016 Jan 21.
4
Palladium-Catalyzed α,β-Dehydrogenation of Esters and Nitriles.钯催化的酯和腈的α,β-脱氢反应。
J Am Chem Soc. 2015 May 13;137(18):5875-8. doi: 10.1021/jacs.5b02243. Epub 2015 Apr 28.
5
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Org Lett. 2015 Apr 3;17(7):1708-11. doi: 10.1021/acs.orglett.5b00480. Epub 2015 Mar 23.
6
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J Am Chem Soc. 2013 Apr 24;135(16):6026-9. doi: 10.1021/ja403188t. Epub 2013 Apr 15.
7
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Org Lett. 2011 Dec 16;13(24):6464-7. doi: 10.1021/ol202766g. Epub 2011 Nov 15.
8
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