Zinc promoted alkylation of olefins with hydrogen

doi:10.3969/j.issn.1000-1565.2017.04.006锌促进的烯烃氢烷基化反应

Abstract

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.

Key words: reductive coupling, C(sp³)—C(sp³)bonds, Zinc

CLC Number:

O621

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.

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.