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Review
. 2016 Oct 21;354(6310):aah5133.
doi: 10.1126/science.aah5133.

Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition

Khoa D Nguyen  1 , Boyoung Y Park  1 , Tom Luong  1 , Hiroki Sato  1 , Victoria J Garza  1 , Michael J Krische  2
Affiliations
Review

Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition

Khoa D Nguyen et al. Science. .

Abstract

α-Olefins are the most abundant petrochemical feedstock beyond alkanes, yet their use in commodity chemical manufacture is largely focused on polymerization and hydroformylation. The development of byproduct-free catalytic C-C bond-forming reactions that convert olefins to value-added products remains an important objective. Here, we review catalytic intermolecular reductive couplings of unactivated and activated olefin-derived nucleophiles with carbonyl partners. These processes represent an alternative to the longstanding use of stoichiometric organometallic reagents in carbonyl addition.

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Figures

Figure 1
Figure 1
Metal catalyzed reductive coupling of unactivated and activated olefin-derived nucleophiles with carbonyl compounds.
Figure 2
Figure 2
Metal catalyzed reductive coupling of α-olefins with carbonyl partners.a aAdCO2H refers to 1-adamantane carboxylic acid. X-Phos = 2-dicyclohexylphosphino-2’,4′,6′-triisopropylbiphenyl
Figure 3
Figure 3
Metal catalyzed reductive coupling of olefins with anhydrides.a a(S,S)-Ph-BPE = 1,2-bis[(2S,5S)-2,5-diphenylphospholano]ethane. DMMS = dimethoxymethylsilane.
Figure 4
Figure 4
Iron catalyzed Prins-Meerwein-Ponndorf-Verley-type olefin-aldehyde reductive coupling.
Figure 5
Figure 5
Metal catalyzed diene-carbonyl reductive coupling. adppf = 1,1-bis-(diphenylphosphino)ferrocene. (R)-DM-SEGPHOS = (R)-(+)-5,5′−bis-[di(3,5-xylyl)phosphino]-4,4′-bi-1,3-benzodioxole. (S)-SEGPHOS = (S)-(−)-5,5′-bis-(diphenylphosphino)-4,4′-bi-1,3-benzodioxole. acac = acetylacetonate.
Figure 6
Figure 6
Alternate regioselectivity and use of cyclic dienes in metal catalyzed carbonyl reductive coupling.a adppb = bis-(diphenylphosphino)butane. biphep = 2,2′-bis-(diphenylphosphino)-1,1′-biphenyl.
Figure 7
Figure 7
Ruthenium(0) catalyzed diene-ketone reductive coupling via hydrogen auto-transfer.a aPCy3 = tricyclohexylphosphine.
Figure 8
Figure 8
Metal catalyzed enyne-carbonyl reductive coupling.a aDMMS = dimethoxymethylsilane. (R)-BINAP = (R)-(+)-2,2′-bis-(diphenylphosphino)-1,1′-binaphthyl
Figure 9
Figure 9
Enantioselective metal catalyzed reductive aldol reactions.a aSee primary literature for the structures of indane-pybox, phebox, taniaphos and AbbasPhos-I.
Figure 10
Figure 10
Metal catalyzed reductive coupling of vinyl azines.a
Figure 11
Figure 11
A departure from preformed organometallic reagents in carbonyl addition.
See this image and copyright information in PMC

References

    1. Frohning CD, Kohlpaintner CW. In: Applied Homogeneous Catalysis with Organometallic Compounds. Cornils B, Herrmann WA, editors. Wiley-VCH; Weinheim: 1996. pp. 29–104.
    1. van Leeuwen PWNM. Homogeneous Catalysis: Understanding the Art. Kluwer; Dordrecht: 2004.
    1. Baier MC, Zuideveld MA, Mecking S. Post-Metallocenes in the Industrial Production of Polyolefins. Angew. Chem. Int. Ed. 2014;53:9722–9744. - PubMed
    1. Cornell CN, Sigman MS. Recent Progress in Wacker Oxidations: Moving toward Molecular Oxygen as the Sole Oxidant. Inorg. Chem. 2007;46:1903–1909. - PubMed
    1. Kablaoui NM, Buchwald SL. Reductive Cyclization of Enones by a Titanium Catalyst. J. Am. Chem. Soc. 1995;117:6785–6786.

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