Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
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.

PubMed Disclaimer

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

Similar articles

See all similar articles

Cited by

See all "Cited by" articles

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.

Publication types

LinkOut - more resources