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Review
. 2018 Jun 27;118(12):6026-6052.
doi: 10.1021/acs.chemrev.8b00213. Epub 2018 Jun 13.

Intermolecular Metal-Catalyzed Reductive Coupling of Dienes, Allenes, and Enynes with Carbonyl Compounds and Imines

Michael Holmes  1 , Leyah A Schwartz  1 , Michael J Krische  1
Affiliations
Review

Intermolecular Metal-Catalyzed Reductive Coupling of Dienes, Allenes, and Enynes with Carbonyl Compounds and Imines

Michael Holmes et al. Chem Rev. .

Abstract

Metal-catalyzed reductive coupling has emerged as an alternative to the use of stoichiometric organometallic reagents in an increasingly diverse range of carbonyl and imine additions. In this review, the use of diene, allene, and enyne pronucleophiles in intermolecular carbonyl and imine reductive couplings are surveyed, along with related hydrogen autotransfer processes.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1.
Figure 1.
Selected milestones in organometallic and carbonyl addition chemistry.
Scheme 1.
Scheme 1.
Nickel(0)-catalyzed diene-aldehyde reductive coupling
Scheme 2.
Scheme 2.
Catalytic mechanism for nickel(0)-catalyzed diene-aldehyde reductive coupling
Scheme 3.
Scheme 3.
Enantioselective nickel(0)-catalyzed diene-aldehyde reductive couplings
Scheme 4.
Scheme 4.
Formaldehyde as electrophile and reductant in nickel(0)-catalyzed reductive couplings to 2substituted dienes
Scheme 5.
Scheme 5.
Nickel(0)-catalyzed diene-imine reductive couplings
Scheme 6.
Scheme 6.
Ruthenium(II)-catalyzed diene-aldehyde reductive couplings mediated by 2-propanol, formic acid or hydrogen auto-transfer
Scheme 7.
Scheme 7.
syn-Diastereo- and enantioselective ruthenium(II)-catalyzed reductive coupling of aldehydes with 2-trialkylsilyl substituted dienes mediated by 2-propanol or hydrogen auto-transfer
Scheme 8.
Scheme 8.
Divergent diastereoselectivity in asymmetric ruthenium(II)-catalyzed butadiene-aldehyde reductive couplings
Scheme 9.
Scheme 9.
Divergent regioselectivity in ruthenium(II)-catalyzed diene-carbonyl reductive couplings
Scheme 10.
Scheme 10.
Ruthenium(0)-catalyzed diene-ketone reductive coupling via hydrogen auto-transfer
Scheme 11.
Scheme 11.
Reversible oxidative coupling pathways in ruthenium(0)-catalyzed diene-ketone reductive coupling
Scheme 12.
Scheme 12.
Ruthenium(0)-catalyzed diene-dione reductive coupling resulting in [4+2] cycloaddition
Scheme 13.
Scheme 13.
Ruthenium(II)-catalyzed diene-imine reductive coupling mediated by 2-propanol or hydrogen auto-transfer
Scheme 14.
Scheme 14.
Ruthenium(0)-catalyzed diene-imine reductive coupling via hydrogen auto-transfer
Scheme 15.
Scheme 15.
Rhodium(I)-catalyzed diene-carbonyl reductive couplings mediated by hydrogen and triethylborane
Scheme 16.
Scheme 16.
Iridium(I)-catalyzed cyclohexadiene-aldehyde reductive coupling mediated by 2-propanol or hydrogen auto-transfer
Scheme 17.
Scheme 17.
Iridium(I)-catalyzed butadiene-aldehyde reductive coupling mediated by 1,4-butanediol or hydrogen auto-transfer
Scheme 18.
Scheme 18.
Iridium(I)-catalyzed reductive coupling of 2-substituted dienes with methanol via hydrogen auto-transfer
Scheme 19.
Scheme 19.
Titanium catalyzed diene-aldehyde reductive coupling mediated by silane
Scheme 20.
Scheme 20.
Copper-catalyzed reductive coupling of 2-azadienes with aryl ketones and imines mediated by silane
Scheme 21.
Scheme 21.
Nickel(0)-catalyzed reductive coupling of chiral nonracemic allenes and aldehydes mediated by triethylsilane
Scheme 22.
Scheme 22.
Ruthenium(II)-catalyzed allene-aldehyde reductive coupling mediated by 2-propanol or hydrogen auto-transfer
Scheme 23.
Scheme 23.
Use of CF3-allenes and fluorinated alcohols in ruthenium(II)-catalyzed allene-aldehyde reductive coupling mediated by 2-propanol or hydrogen auto-transfer
Scheme 24.
Scheme 24.
Alkynes as latent allenes in ruthenium(0) and ruthenium(II) catalyzed allene-aldehyde reductive couplings via hydrogen auto-transfer
Scheme 25.
Scheme 25.
Ruthenium(II)-catalyzed allene-imine reductive coupling mediated by 2-propanol
Scheme 26.
Scheme 26.
Iridium(I)-catalyzed allene-aldehyde reductive coupling mediated by hydrogen, 2propanol or hydrogen auto-transfer
Scheme 27.
Scheme 27.
Enantioselective carbonyl tert-prenylation via iridium(I)-catalyzed dimethylallenealdehyde reductive coupling mediated by 2-propanol or hydrogen auto-transfer
Scheme 28.
Scheme 28.
Iridium(I)-catalyzed reductive coupling of 1,1disubstituted allenes via methanol-mediated hydrogen auto-transfer
Scheme 29:
Scheme 29:
Palladium catalyzed allene-aldehyde reductive coupling mediated by stannous chloride
Scheme 30.
Scheme 30.
Palladium(0)-catalyzed allene-anhydride reductive coupling mediated by silane
Scheme 31.
Scheme 31.
Copper(I)-catalyzed allene-ketone reductive coupling mediated by silane
Scheme 32.
Scheme 32.
Regiodivergent copper(I)-catalyzed allene-imine reductive coupling mediated by silane
Scheme 33.
Scheme 33.
Nickel(0)-catalyzed enyne-aldehyde reductive coupling mediated by triethylborane
Scheme 34.
Scheme 34.
Ligand-dependent inversion of regioselectivity in nickel(0)-catalyzed enyne-aldehyde reductive coupling mediated by silane
Scheme 35.
Scheme 35.
Enantioselective rhodium(I)-catalyzed enyne-aldehyde and enyne-ketone reductive coupling mediated by hydrogen
Scheme 36.
Scheme 36.
Catalytic mechanism for rhodium(I)-catalyzed enyne-carbonyl reductive coupling mediated by hydrogen
Scheme 37.
Scheme 37.
Asymmetric rhodium(I)-catalyzed enyne-imine reductive coupling mediated by hydrogen
Scheme 38.
Scheme 38.
Ruthenium(II)-catalyzed enyne-aldehyde reductive coupling mediated by 2-propanol and hydrogen auto-transfer
Scheme 39.
Scheme 39.
anti-Diastereoselective iridium(I)-catalyzed enyne-aldehyde reductive coupling mediated by formic acid or hydrogen auto-transfer
Scheme 40.
Scheme 40.
Diastereoselective copper(I)-catalyzed enyne-ketone reductive coupling mediated by silane
Scheme 41.
Scheme 41.
Total synthesis of bryostatin 7 via asymmetric rhodium- and iridium-catalyzed hydrogenative and transfer-hydrogenative reductive couplings, respectively
Scheme 42.
Scheme 42.
Total syntheses of trienomycins A and F and 6-deoxyerythronolide B via rutheniumcatalyzed syn-diastereo- and enantioselective diene-carbonyl reductive coupling mediated by hydrogen auto-transfer
Scheme 43.
Scheme 43.
Syntheses of the C8-C22 substructure of rhizopodin via enantioselective iridium-catalyzed allene-aldehyde reductive coupling via hydrogen auto-transfer
Scheme 44.
Scheme 44.
Catalytic reductive coupling for carbonyl addition
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References

    1. Frankland E Isolation of Organic Radicals. Ann 1849, 71, 171–213.
    1. For a historical review, see: Seyferth D Zinc Alkyls, Edward Frankland, and the Beginnings of MainGroup Organometallic Chemistry. Organometallics 2001, 20, 2940–2955.
    1. For a historical review, see: Thayer JS Historical Origins of Organometallic Chemistry. J. Chem. Educ. 1969, 46, 764–765.
    1. Wanklyn JA Ueber die Bildung der Propionsäure aus Kohlensäure und eine Aethylverbindung. Ann. Chem. Pharm 1858, 107, 125–128.
    1. For a historical review, see: Seyferth D Alkyl and Aryl Derivatives of the Alkali Metals: Useful Synthetic Reagents as Strong Bases and Potent Nucleophiles. 1. Conversion of Organic Halides to Organoalkali-Metal Compounds. Organometallics 2006, 25, 2–24.

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