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由硼鎓阳离子和B(CF)介导的炔烃的高选择性催化硼氢化反应

Highly selective catalytic -hydroboration of alkynes mediated by borenium cations and B(CF).

作者信息

McGough John S, Butler Samuel M, Cade Ian A, Ingleson Michael J

机构信息

University of Manchester , Oxford Road , Manchester M13 9PL. , UK . Email:

出版信息

Chem Sci. 2016 May 1;7(5):3384-3389. doi: 10.1039/c5sc04798f. Epub 2016 Feb 12.

DOI:10.1039/c5sc04798f
PMID:29997833
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6006955/
Abstract

The -hydroboration of terminal alkynes mediated by borenium cations [NHC(9-BBN)] (NHC = N-heterocyclic carbene, 9-BBN = 9-borabicyclo(3.3.1)nonane) exclusively affords -vinylboranes. NHCs and chelating dialkyl substituents on the borenium cation and "non"-basic anions were essential to preclude alternative reactions including dehydroboration. Deuterium labelling studies indicate the mechanism involves addition of the boron electrophile to the alkyne and transfer of hydride to the opposite face of the activated alkyne. -Hydroboration proceeds with only catalytic amounts of B(CF) or [PhC][B(CF)] to activate the (NHC)9-BBN(H) precursor with the borenium regenerated in the hydride transfer step. The NHC can be removed from the -hydroborated products by the addition of EtO-BF providing access to vinylBBN species effective for Suzuki-Miyaura couplings to generate -alkenes. Combinations of catalytic B(CF) and stoichiometric [HB(CF)] also lead to -hydroboration of terminal alkynes to form -isomers of [arylCH[double bond, length as m-dash]CHB(CF)].

摘要

由硼正离子[NHC(9-BBN)]（NHC = N-杂环卡宾，9-BBN = 9-硼双环(3.3.1)壬烷）介导的末端炔烃的硼氢化反应专一性地生成β-乙烯基硼烷。硼正离子上的NHC和螯合二烷基取代基以及“非”碱性阴离子对于排除包括脱氢硼化在内的其他反应至关重要。氘标记研究表明，该反应机理涉及硼亲电试剂加成到炔烃上以及氢负离子转移到活化炔烃的相反面。β-硼氢化反应仅需催化量的B(CF₃)₃或[Ph₃C][B(CF₃)₄]来活化(NHC)9-BBN(H)前体，硼正离子在氢负离子转移步骤中再生。通过加入Et₃O⁺BF₄⁻，可以从β-硼氢化产物中除去NHC，从而得到对铃木-宫浦偶联反应有效的乙烯基BBN物种，以生成β-烯烃。催化量的B(CF₃)₃和化学计量的[HB(CF₃)₃]的组合也会导致末端炔烃的β-硼氢化反应，形成[芳基CH=CHB(CF₃)₂]的β-异构体。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/edea/6006955/8b09bc3f5c76/c5sc04798f-s7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/edea/6006955/99253f07e5cd/c5sc04798f-f1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/edea/6006955/fb692a63488d/c5sc04798f-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/edea/6006955/8b09bc3f5c76/c5sc04798f-s7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/edea/6006955/99253f07e5cd/c5sc04798f-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/edea/6006955/2b1cdb1bcc79/c5sc04798f-s1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/edea/6006955/b0f8e7b57715/c5sc04798f-f2.jpg
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本文引用的文献

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Chem Sci. 2015 Mar 1;6(3):2010-2015. doi: 10.1039/c4sc03675a. Epub 2015 Jan 26.
2
Advanced 1,1-carboboration reactions with pentafluorophenylboranes.与五氟苯基硼烷的高级1,1-碳硼化反应。
Chem Sci. 2016 Jan 1;7(1):56-65. doi: 10.1039/c5sc03282b. Epub 2015 Oct 8.
3
Facile Arylation of Four-Coordinate Boron Halides by Borenium Cation Mediated Boro-desilylation and -destannylation.
钯/ Senphos 催化 1,3-烯炔的 -氢硼化反应的机理：支持非经典的外球氧化加成途径的实验和计算证据。
J Org Chem. 2023 Feb 17;88(4):2415-2424. doi: 10.1021/acs.joc.2c02841. Epub 2023 Feb 8.
4
Copper-catalyzed radical -selective hydroboration of ynamides with -heterocyclic carbene boranes.铜催化的异酰胺与杂环卡宾硼烷的自由基选择性硼氢化反应。
iScience. 2022 Aug 17;25(9):104977. doi: 10.1016/j.isci.2022.104977. eCollection 2022 Sep 16.
5
Activation of Si-H and B-H bonds by Lewis acidic transition metals and p-block elements: same, but different.路易斯酸性过渡金属和p区元素对Si-H键和B-H键的活化作用：相同却又不同。
Chem Sci. 2022 Jun 6;13(25):7392-7418. doi: 10.1039/d2sc02324e. eCollection 2022 Jun 29.
6
Recent advances in transition metal-free catalytic hydroelementation (E = B, Si, Ge, and Sn) of alkynes.炔烃的无过渡金属催化氢元素加成反应（E = B、Si、Ge和Sn）的最新进展。
RSC Adv. 2020 Dec 7;10(71):43539-43565. doi: 10.1039/d0ra07768b. eCollection 2020 Nov 27.
7
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10
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通过硼正离子介导的硼脱硅基化和脱锡基化实现四配位硼卤化物的简便芳基化反应。
Organometallics. 2015 Dec 28;34(24):5767-5774. doi: 10.1021/acs.organomet.5b00857. Epub 2015 Dec 8.
4
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5
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6
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7
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8
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Chemistry. 2014 Sep 26;20(40):12874-80. doi: 10.1002/chem.201403614. Epub 2014 Aug 19.