Page 1
S1
ExtremelyEfficientHydroborationofKetonesandAldehydesbyCopperCarbeneCatalysis
ShararehBagherzadehandNealP.Mankad*
DepartmentofChemistry,UniversityofIllinoisatChicago,845W.TaylorSt.MC111,Chicago,IL60607USA.
*[email protected]
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
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
S3
Figure S1. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-iodoacetophenone at 10min.
Page 4
S4
Figure S2. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4'- (trifluoromethyl)acetophenone at 10min.
Page 5
S5
Figure S3. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-methoxyacetophenone at 10min.
Page 6
S6
Figure S4. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 3-methyl 2-butanone at 10min.
Page 7
S7
Figure S5. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of benzophenone at 10min.
Page 8
S8
Figure S6. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4- bromobenzaldehyde at 10min.
Page 9
S9
Figure S7. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 2,4,6- trimethylbenzaldehyde at 10min.
Page 10
S10
Figure S8. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 2- iodoacetophenone at 10min.
Page 12
S12
Figure S9. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-acetylbenzaldehyde at 10min.
Page 13
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
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
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
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
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
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
S19
Figure S16. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-Iodoacetophenone at 1h.
Page 20
S20
Figure S17. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4'- (trifluoromethyl)acetophenone at 1h.
Page 21
S21
Figure S18. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-methoxyacetophenone at 1h.
Page 22
S22
Figure S19. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of benzophenone at 1h.
Page 23
S23
Figure S20. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 3-methyl 2-butanone at 1h.
Page 24
S24
Figure S21. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 4-bromobenzaldehyde at 1h.
Page 25
S25
Figure S22. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 2, 4,6- trimethylbenzaldehyde at 1h.
Page 26
S26
Figure S23. 1H NMR (top) and 11B NMR (bottom) spectra resulting from catalytic hydroboration
of 2-iodoacetophenone at 1h.
Page 27
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
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
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
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
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
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
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
S34
Figure S31. 1H NMR (top) and 11B NMR (bottom) spectra of isolated 2-(benzhydryloxy)-4,4,5,5-
tetramethyl-1,3,2-dioxaborolane.