Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh

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ExtremelyEfficientHydroborationofKetonesandAldehydesbyCopperCarbeneCatalysis

ShararehBagherzadehandNealP.Mankad*

DepartmentofChemistry,UniversityofIllinoisatChicago,845W.TaylorSt.MC111,Chicago,IL60607USA.

*npm@uic.edu

ElectronicSupplementaryInformation

Generalconsiderations:AllreactionswereconductedunderpurifiedN2usinginagloveboxandaSchlenkline.Deuteratedbenzene(C6D6)wasdegasedbyrepeatedfreeze-pump-thawcyclesandstoredoveractivated3-Åmolecularsievespriortouse.1Hand11BNMRspectrawererecordedusingBrukerAvance400-MHzNMRspectrometer.NMRspectrawererecordedatroomtemperature,andchemicalshiftswerereferencedtoresidualsolventpeak.11BNMRchemicalshiftswerereferencedtoexternalpinacolborane(29.01and27.6ppm).Literaturemethodswasusedtosynthesize(IPr)CuOtBu.1Allotherreagentswerepurchasedfromcommercialvendorsandusedwithoutfurtherpurification.

Generalcatalyticprocedure:Intheglovebox,ascintillationvialwaschargedwith(IPr)CuOtBu(1.5mg,0.00285mmol),andC6D6(6mL)wasadded.Another20-mLscintillationvialwaschargedwithastirbarandsubstrate(0.952mmol).ThesubstratewasdissolvedinC6D6(5mL),andthenpinacolborane(138µL,0.952mmol),mesitylene(132.6µL,0.952mmol)andinsomecasesadditive(0.952mmol)wereaddedtothissolution.Thenanaliquotofthe(IPr)CuOtBustocksolution(2mL)wasaddedtothereactionvial,andtheresultingmixturewasstirredatroomtemperaturefor10minand1h(asindicatedinthemanuscript).AliquotsofthereactionsolutionwastransferredtoNMRtubes,and1Hand11BNMRspectra(seebelow)weretakentomonitorreactionprogress.Separatecatalyticrunsperformedbymultipleresearcherswerereproducedtowithin±2%.

Isolationof2-(1-(4-iodophenyl)ethoxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane:Intheglovebox,ascintillationvialwaschargedwith(IPr)CuOtBu(1mg,0.002mmol),andwasdissolvedinC6D6(2mL).Another20-mLscintillationvialwaschargedwithastirbarand4-iodoacetophenone(0.234g,0.952mmol).ThesubstratewasdissolvedinC6D6(2mL),andthenpinacolborane(138µL,0.952mmol)wasaddedtothissolution.Thenanaliquoteofthecatalyststocksolution(1mL)wasaddedtothesolutiontothereactionvial,andtheresultingmixture

1 N. P. Mankad, D. S. Laitar, & J. P. Sadighi, Organometallics, 2004, 23, 3369-3371.

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2016

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wasstirredatroomtemperaturefor1h.Thevolatileswereremovedtoaffordtheproduct:0.25g,70%.

Isolationof2-(benzhydryloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane:Intheglovebox,ascintillationvialwaschargedwith(IPr)CuOtBu(1mg,0.002mmol),andwasdissolvedinC6D6(2mL).Another20-mLscintillationvialwaschargedwithastirbarandbenzophenone(0.173g,0.952mmol).ThesubstratewasdissolvedinC6D6(2mL),andthenpinacolborane(138µL,0.952mmol)wasaddedtothissolution.Analiquotofthecatalyststocksolution(1mL)wasaddedtothesolutiontothereactionvial,andtheresultingmixturewasstirredatroomtemperaturefor1h.Thevolatileswereremovedtoaffordtheproduct:0.20g,yield:68%.

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Figure S1. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-iodoacetophenone at 10min.

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Figure S2. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4'- (trifluoromethyl)acetophenone at 10min.

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Figure S3. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-methoxyacetophenone at 10min.

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Figure S4. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 3-methyl 2-butanone at 10min.

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Figure S5. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of benzophenone at 10min.

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Figure S6. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4- bromobenzaldehyde at 10min.

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Figure S7. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 2,4,6- trimethylbenzaldehyde at 10min.

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Figure S8. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 2- iodoacetophenone at 10min.

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Figure S9. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-acetylbenzaldehyde at 10min.

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Figure S10. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-iodoacetophenone in the presence of 1-dodecene at 10min.

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Figure S11. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-iodoacetophenone additive 1-decyne at 10min.

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Figure S12. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-iodoacetophenone additive 1-chlorododecene at 10min.

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Figure S13. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-iodoacetophenone in the presence of acetonitrile at 10min.

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Figure S14. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-iodoacetophenone in the presence of methylbenzoate at 10min.

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Figure S15. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-iodoacetophenone in the presence of pyridine at 10min.

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Figure S16. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-Iodoacetophenone at 1h.

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Figure S17. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4'- (trifluoromethyl)acetophenone at 1h.

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Figure S18. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-methoxyacetophenone at 1h.

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Figure S19. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of benzophenone at 1h.

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Figure S20. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 3-methyl 2-butanone at 1h.

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Figure S21. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-bromobenzaldehyde at 1h.

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Figure S22. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 2, 4,6- trimethylbenzaldehyde at 1h.

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Figure S23. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 2-iodoacetophenone at 1h.

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Figure S24. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-iodoacetophenone in the presence of 1-dodecene at 1h.

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Figure S25. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-iodoacetophenone in the presence of 1-decyne at 1h.

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Figure S26. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-iodoacetophenone in the presence of acetonitrile at 1h.

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Figure S27. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-iodoacetophenone in the presence of methylbenzoate at 1h.

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Figure S28. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-iodoacetophenone in the presence of 1-chlorododecene at 1h.

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Figure S29. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration

of 4-iodoacetophenone in the presence of pyridine at 1h.

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Figure S30. 1H NMR (top) and 11B NMR (bottom) spectra of isolated 2-(1-(4-iodophenyl)ethoxy)-

4,4,5,5-tetramethyl-1,3,2-dioxaborolane.

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Figure S31. 1H NMR (top) and 11B NMR (bottom) spectra of isolated 2-(benzhydryloxy)-4,4,5,5-

tetramethyl-1,3,2-dioxaborolane.