Zinc promoted alkylation of olefins with hydrogen

  • WAN Xiaolong ,
  • CHEN Yanchi ,
  • SUN Yuren ,
  • QIAN Qun
Expand
  • School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China

Received date: 2016-12-10

  Online published: 2017-07-25

Abstract

The construction of the quaternary carbon center has been a difficult and hot issue in organic synthesis.In particular, the synthesis of quaternary carbon center by the formation of the intermolecular C(sp3)—C(sp3)bond with cheap tert-alkyl bromides is rarely reported.Recently, our group reported that nickel-catalyzed reductive coupling of aryl bromides with tertiary alkyl halides.Based on this, we proposed that using cheap reductive metal as a free radical initiator, mediated the formation of tertiary carbon free radicals from tert-alkyl bromides, and then the free radical captured by olefin to build C(sp3)—C(sp3)bond quaternary carbon center efficiently.Herein, we report the application of this strategy in constructing quaternary carbon center by Zn powder mediated reductive coupling reaction.

Cite this article

WAN Xiaolong , CHEN Yanchi , SUN Yuren , QIAN Qun . Zinc promoted alkylation of olefins with hydrogen[J]. Journal of Hebei University(Natural Science Edition), 2017 , 37(4) : 364 -368 . DOI: 10.3969/j.issn.1000-1565.2017.04.006锌促进的烯烃氢烷基化反应

References

[1] TERAO J, TODO H, BEGUM S A, et al.Copper-catalyzed cross-coupling reaction of grignard reagents with primary-alkyl halides: remarkable effect of 1-Phenylpropyne [J].Angewandte Chemie International Edition, 2007, 46: 2086-2089.DOI: 10.1002/anie.200603451.
[2] REN P, STERN L A, HU X L.Copper-catalyzed cross-coupling of functionalized alkyl halides and tosylates with secondary and tertiary alkyl grignard reagents [J].Angewandte Chemie International Edition, 2012, 51: 9110-9113.DOI: 10.1002/anie.201204275.
[3] YANG C T, ZHANG Z Q, LIANG J, et al.Copper-catalyzed cross-coupling of nonactivated secondary alkyl halides and tosylates with secondary alkyl grignard reagents [J].Journal of the American Chemical Society,2012, 134: 11124-11127.DOI: 10.1021/ja304848n.
[4] HINTERMANN L, XIAO L, LABONNE A.A general and selective copper-catalyzed cross-coupling of tertiary grignard reagents with azacyclic electrophiles [J].Angewandte Chemie International Edition, 2008, 47: 8246-8250.DOI: 10.1002/anie.200803312.
[5] IWASAKI T, TAKAGAWA H, SINGH S P, et al.Co-catalyzed cross-coupling of alkyl halides with tertiary alkyl grignard reagents using a 1,3-butadiene additive [J].Journal of the American Chemical Society, 2013, 135: 9604-9607.DOI: 10.1021/ja404285b.
[6] THAPA S, KAFLE A, GURUNG S K, et al.Ligand-free copper-catalyzed negishi coupling of alkyl-, aryl-, and alkynylzinc reagents with heteroaryl iodides [J].Angewandte Chemie International Edition, 2015, 54: 8236-8240.DOI: 10.1002/anie.201502379.
[7] MARTIN R, BUCHWALD S L.An improved protocol for the Pd-catalyzed α-arylation of aldehydes with aryl halides [J].Org Lett, 2008, 10: 4561-4564.DOI: 10.1021/ol8017775.
[8] JOSHI-PANGU A, WANG C Y, BISCOE M R,Nickel-catalyzed kumada cross-coupling reactions of tertiary alkylmagnesium halides and aryl bromides/triflates [J].Journal of the American Chemical Society, 2011, 133: 8478-8481.DOI: 10.1021/ja202769t.
[9] ZULTANSKI S L, FU G C.Nickel-catalyzed carbon-carbon bond-forming reactions of unactivated tertiary alkyl halides: suzuki arylations [J].Journal of the American Chemical Society, 2013, 135: 624-627.DOI: 10.1021/ja311669p.
[10] GHORAI S K, JIN M, HATAKEYAMA T, et al.Cross-coupling of non-activated chloroalkanes with aryl grignard reagents in the presence of iron/N-heterocyclic carbene catalysts [J].Org Lett,2012, 14:1066-1069.DOI: 10.1021/ol2031729.
[11] TSUJI T, YORIMITSU H, OSHIMA K. Cobalt-catalyzed coupling reaction of alkyl halides with allylic grignard reagents [J].Angewandte Chemie International Edition, 2002, 41: 4137-4139.DOI: 10.1002/1521-3773(20021104)41:21<4137::AID-ANIE4137>3.0.CO;2-0.
[12] DUNSFORD J J, CLARK E R, INGLESON M J.Direct C(sp2)—C(sp3)cross-coupling of diaryl zinc reagents with benzylic, primary, secondary, and tertiary alkyl halides [J].Angewandte Chemie International Edition, 2015, 54: 5688-5692.DOI: 10.1002/anie.201411403.
[13] HUANG C Y, DOYLE A G.Electron-deficient olefin ligands enable generation of quaternary carbons by Ni-catalyzed cross-coupling [J].Journal of the American Chemical Society, 2015, 137: 5638-5641.DOI: 10.1021/jacs.5b02503.
[14] WANG X, WANG S L, XUE W C, et al.Nickel-catalyzed reductive coupling of aryl bromides with tertiary alkyl halides [J].Journal of the American Chemical Society, 2015, 137: 11562-11565.DOI: 10.1021/jacs.5b06255.
[15] ZHAO C L, JIA X, WANG X, et al.Ni-catalyzed reductive coupling of alkyl acids with unactivated tertiary alkyl and glycosyl halides [J].Journal of the American Chemical Society, 2014, 136: 17645-17651.DOI: 10.1021/ja510653n.
[16] XU H L, ZHANG Y W, WANG S L, et al. Optimization of ligands in nickel-catalyzed cross-coupling of alkyl halides [J].Journal of Shanghai University(Natural Science Edition)2014, 20: 221-227.DOI: 10.3969/j.issn.1007-2861.2013.07.006.
[17] QIN T, MALINS L R, EDWARDS J T, et al.Nickel-catalyzed barton decarboxylation and giese reactions: a practical take on classic transforms [J].Angewandte Chemie, 2017, 129: 266-271.DOI: 10.1002/ange.201609662.
[18] DUDNIK A S, FU G C.Nickel-catalyzed coupling reactions of alkyl electrophiles, including unactivated tertiary halides, to generate carbon-boron bonds [J].Journal of the American Chemical Society 2012, 134: 10693-10697.DOI: 10.1021/ja304068t.
[19] ZHANG J, LI Y, ZHANG F, et al.Generation of alkoxyl radicals by photoredox catalysis enables selective C(sp3)-H functionalization under mild reaction conditions [J]. Angewandte Chemie International Edition, 2016, 55: 1872-1875.DOI: 10.1002/anie.201510014.
Outlines

/

〈 〉