extremely efficient hydroboration of ketones and aldehydes by … · 2016-02-08 · s1 extremely...
TRANSCRIPT
![Page 1: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/1.jpg)
S1
ExtremelyEfficientHydroborationofKetonesandAldehydesbyCopperCarbeneCatalysis
ShararehBagherzadehandNealP.Mankad*
DepartmentofChemistry,UniversityofIllinoisatChicago,845W.TaylorSt.MC111,Chicago,IL60607USA.
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
![Page 2: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/2.jpg)
S2
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%.
![Page 3: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/3.jpg)
S3
Figure S1. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-iodoacetophenone at 10min.
![Page 4: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/4.jpg)
S4
Figure S2. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4'- (trifluoromethyl)acetophenone at 10min.
![Page 5: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/5.jpg)
S5
Figure S3. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-methoxyacetophenone at 10min.
![Page 6: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/6.jpg)
S6
Figure S4. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 3-methyl 2-butanone at 10min.
![Page 7: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/7.jpg)
S7
Figure S5. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of benzophenone at 10min.
![Page 8: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/8.jpg)
S8
Figure S6. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4- bromobenzaldehyde at 10min.
![Page 9: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/9.jpg)
S9
Figure S7. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 2,4,6- trimethylbenzaldehyde at 10min.
![Page 10: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/10.jpg)
S10
Figure S8. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 2- iodoacetophenone at 10min.
![Page 11: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/11.jpg)
S11
![Page 12: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/12.jpg)
S12
Figure S9. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-acetylbenzaldehyde at 10min.
![Page 13: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/13.jpg)
S13
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.
![Page 14: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/14.jpg)
S14
Figure S11. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-iodoacetophenone additive 1-decyne at 10min.
![Page 15: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/15.jpg)
S15
Figure S12. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-iodoacetophenone additive 1-chlorododecene at 10min.
![Page 16: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/16.jpg)
S16
Figure S13. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-iodoacetophenone in the presence of acetonitrile at 10min.
![Page 17: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/17.jpg)
S17
Figure S14. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-iodoacetophenone in the presence of methylbenzoate at 10min.
![Page 18: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/18.jpg)
S18
Figure S15. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-iodoacetophenone in the presence of pyridine at 10min.
![Page 19: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/19.jpg)
S19
Figure S16. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-Iodoacetophenone at 1h.
![Page 20: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/20.jpg)
S20
Figure S17. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4'- (trifluoromethyl)acetophenone at 1h.
![Page 21: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/21.jpg)
S21
Figure S18. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-methoxyacetophenone at 1h.
![Page 22: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/22.jpg)
S22
Figure S19. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of benzophenone at 1h.
![Page 23: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/23.jpg)
S23
Figure S20. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 3-methyl 2-butanone at 1h.
![Page 24: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/24.jpg)
S24
Figure S21. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-bromobenzaldehyde at 1h.
![Page 25: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/25.jpg)
S25
Figure S22. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 2, 4,6- trimethylbenzaldehyde at 1h.
![Page 26: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/26.jpg)
S26
Figure S23. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 2-iodoacetophenone at 1h.
![Page 27: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/27.jpg)
S27
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.
![Page 28: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/28.jpg)
S28
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.
![Page 29: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/29.jpg)
S29
Figure S26. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-iodoacetophenone in the presence of acetonitrile at 1h.
![Page 30: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/30.jpg)
S30
Figure S27. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-iodoacetophenone in the presence of methylbenzoate at 1h.
![Page 31: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/31.jpg)
S31
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.
![Page 32: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/32.jpg)
S32
Figure S29. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-iodoacetophenone in the presence of pyridine at 1h.
![Page 33: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/33.jpg)
S33
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.
![Page 34: Extremely Efficient Hydroboration of Ketones and Aldehydes by … · 2016-02-08 · S1 Extremely Efficient Hydroboration of Ketones and Aldehydes by Copper Carbene Catalysis Sharareh](https://reader036.vdocuments.us/reader036/viewer/2022081515/5ed8b1d46714ca7f47686644/html5/thumbnails/34.jpg)
S34
Figure S31. 1H NMR (top) and 11B NMR (bottom) spectra of isolated 2-(benzhydryloxy)-4,4,5,5-
tetramethyl-1,3,2-dioxaborolane.