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p p L L L L Regioselective Aromatic Borylation in an Inert Solvent
Man Kin Tse, Jian-Yang Cho, and Milton R. Smith, III*
Department of Chemistry, Michigan State University, East Lansing, MI 48824
Supporting Information Experimental Section
General Considerations. Catalytic reaction mixtures were prepared in a glove box. Cp*Rh( h4- C 6 M e 6 ) w a s p r e p a r e d a c c o r d i n g t o t h e l i t e r a t u r e m e t h o d . P P h 3 w a s r e c r y s t a l l i z e d f r o m p e n t a n e b e f o r e u s e . H B P i n w a s p u r c h a s e d f r o m A l d r i c h , a n d f u r t h e r p u r i f i e d b y s t i r r i n g w i t h P P h 3 t o r e m o v e B H 3 . H B P i n w a s v a c u u m t r a n s f e r r e d a t r o o m t e m p e r a t u r e t o give the borane as a clear viscous liquid. Cyclohexane (spectrophotometric grade) was purchased from Mallinckrodt and was washed with equal volumes of conc. H2SO4 until the washings were colorless, followed by water (3 x 100 mL), 5% NaOH (100 mL), and again water (3 x 100 mL) until the pH of the aqueous phase was neutral. After preliminary drying with MgSO4 and refluxing over Na, the cyclohexane was vacuum transferred at room temperature and passed through a column of activated alumina. Benzene, 1,3-dimethoxybenzene, and 3-methylanisole were distilled from sodium metal. m-Xylene was distilled and passed through a column of activated alumina. 1,3-Bis(trifluoromethyl)benzene and 1,3-dichlorobenzene were distilled, dried over 4 sieves, and vacuum transferred to an air free flask. Veratrole was distilled from CaH2 under N2. N,N-Dimethyl-m-anisidine, N,N,N,N-tetramethyl-1,3-phenylenediamine and N-tri-iso-propylpyrrole were prepared according to literature methods and vacuum distilled before use. CDCl3 was vacuum transferred after drying over 3 sieves.
1H and 13C NMR spectra were recorded on a Varian Inova-300 and Varian Germini-300 spectrometers (300.11 and 75.43 MHz respectively) and referenced to residual solvent signals. 11B spectra were recorded on a Varian VXR-300 operating at 96.29 MHz and were referenced to neat BF3.Et2O as the external standard. Elemental analyses were performed at Michigan State University using a Perkin Elmer Series II CHNS/O Analyzer 2400. GC-MS data were obtained using an HP G1800B GCD system and GC-FID data wer>
Transfer interrupted!
. HRMS data were obtained at the Michigan State University Mass Spectrometry Facility, which is supported, in part, by a grant (DRR-00480) from the Biotechnology Research Technology Program, National Center for Research Resources, National Institutes of Health.
Arylboronate Ester Syntheses
The general procedure for the synthesis of arylboronate esters, catalyzed by Cp*Rh( h4 - C 6 M e 6 ) , i s i l l u s t r a t e d f o r t h e s y n t h e s i s o f 5 - ( 4 , 4 , 5 , 5 - t e t r a m e t h y l - 1 , 3 , 2 - d i o x a b o r o l y l ) - 1 , 3 - d i m e t h o x y b e n z e n e . C p * R h ( h4 - C 6 M e 6 ) ( 5 . 0 m g , 0 . 0 1 2 m m o l ) , 1 , 3 - d i m e t h o x y b e n z e n e ( 9 7 m g , 0 . 7 0 m m o l ) a n d H B P i n ( 2 6 9 m g , 2 . 1 0 m m o l ) w e r e d i s s o l v e d i n c y c l o h e x a n e ( 1 m L ) and transferred to an air-free flask. After heating for 32 h at 150 C, the product ratio of 1,3,5-C6H3(OMe)2(BPin):1,3,4-C6H3(OMe)2(BPin), determined by GC-FID of the crude reaction mixture, was 89:11. The solvent was then removed under vacuum at room temperature, and the residue was chromatographed on silica gel (60-200 mesh) column, using hexanes to hexanes:ethyl acetate (9:1) as the gradient eluent. Solvent removal gave 1,3,5-C6H3(OMe)2(BPin) as a white solid (114 mg, 62% based on 1,3-dimethoxybenze n e ) . m p 8 8 - 9 0 C . R f = 0 . 4 0 ( h e x a n e s : e t h y l a c e t a t e = 9 : 1 ) . 1 H N M R ( C D C l 3 ) d 1 . 3 2 ( s , 1 2 H , B O 2 C 6 H 1 2 ) , 3 . 7 9 ( s , 6 H , 2 O C H 3 ) , 6 . 5 5 ( t , J = 2 . 4 H z , 1 H ) , 6 . 9 3 ( d , J = 2 . 4 H z , 2 H ) . 1 3 C N M R ( C D C l 3 ) d 2 4 . 8 2 , 5 5 . 4 0 , 8 3 . 8 7 , 1 0 4 . 5 0 , 1 1 1 . 5 3 , 1 6 0 . 3 5 . 1 1 B N M R ( C D C l 3 ) d 3 0 . 8 . E l e m e n t a l a n a l y s i s f o r C 1 4 H 2 1 B O 4 c a l c d . C ( 6 3 . 6 6 % ) , H ( 8 . 0 1 % ) , N ( 0 . 0 0 % ) . F o u n d C ( 6 3 . 5 8 % ) , H ( 8 . 2 5 % ) , N ( 0 . 0 1 % ) . G C - M S ( m / z ) 2 6 4 . 1 , 3 , 4 - C 6 H 3 ( O M e ) 2 ( B P i n ) w a s i s o l a t e d a s a c o l o r l e s s o i l ( 3 m g , 2 % b a s e d o n 1 , 3 - d i m t h o x y b e n z e n e ) . R f = 0 . 1 7 ( h e x a n e s : e t h y l a c e t a t e = 9 : 1 ) . 1 H N M R ( C D C l 3 ) d 1 . 3 1 ( s , 1 2 H , B O 2 C 6 H 1 2 ) , 3 . 7 9 ( s , 3 H , O C H 3 ) , 3 . 8 0 ( s , 3 H , O C H 3 ) , 6 . 3 8 ( d , J = 2 . 2 H z , 1 H ) , 6 . 4 6 ( d d , J = 8 . 1 , 2 . 2 H z , 1 H ) , 7 . 6 2 ( d , J = 8 . 1 H z , 1 H ) . 1 3 C N M R ( C D C l 3 ) d 2 4 . 7 9 , 5 5 . 2 3 , 5 5 . 7 4 , 8 3 . 1 2 , 9 8 . 0 2 , 1 0 4 . 3 4 , 1 3 8 . 3 5 , 1 6 3 . 6 2 , 1 6 5 . 9 3 . 1 1 B N M R ( C D C l 3 ) d 3 0 . 8 . G C - M S ( m / z ) 2 6 4 .
( 4 , 4 , 5 , 5 - T e t r a m e t h y l - 1 , 3 , 2 - d i o x a b o r o l y l ) b e n z e n e . M e t h o d 1 : B o r y l a t i o n o f b e n z e n e ( 1 0 9 m g , 1 . 4 m m o l ) w i t h H B P i n ( 4 5 m g , 0 . 3 5 m m o l ) w a s c a t a l y z e d b y C p * R h ( h4 - C 6 M e 6 ) ( 5 . 0 m g , 0 . 0 1 2 mmol) in cyclohexane (0.5 mL) in a J. Young NMR tube at 150 C for 38 h. The product ratio of PhBPin, 1,3-C6H4(BPin)2 and 1,4-C6H4(BPin)2, determined by GC-FID of the crude reaction mixture, was 93:5:2. PhBPin (42 mg, 59%) was isolated as colorless oil after chromatography on silica gel using hexanes as the eluent. Rf = 0.17 (hexanes). 1H NMR (CDCl3) d 1 . 3 5 ( s , 1 2 H , B O 2 C 6 H 1 2 ) , 7 . 3 4 - 7 . 3 9 ( m , 2 H ) , 7 . 4 3 - 7 . 4 9 ( m , 1 H ) , 7 . 8 1 - 7 . 8 4 ( m , 2 H ) . G C - M S ( m / z ) 2 0 4 . M e t h o d 2 : C a t a l y t i c b o r y l a t i o n o f b e n z e n e ( 6 0 m g , 0 . 7 7 m m o l ) w i t h H B P i n ( 9 0 m g , 0 . 7 0 m m o l ) c a t a l y z e d b y C p * R h ( h4 - C 6 M e 6 ) ( 5 . 9 m g , 0 . 0 1 4 m m o l ) i n c y c l o hexane (0.5 mL) at 150 C for 87 h. PhBPin (59 mg, 41%) was isolated as a colorless oil. An isomer mixture of diborylated products C6H4(BPin)2 was also isolated (39 mg, 33%). m-C6H4(BPin)2:p-C6H4(BPin)2 = 2:1 (determined by 1H NMR integrations). m-C6H4(BPin)2: Rf = 0.09 (hexanes). 1H NMR (CDCl3) d 1 . 3 2 ( s , 2 4 H , 2 B O 2 C 6 H 1 2 ) , 7 . 3 6 ( t , J = 7 . 3 H z , 1 H ) , 7 . 8 8 ( d d , J = 7 . 3 , 1 . 4 H z , 2 H ) , 8 . 2 6 ( s , 1 H ) . p - C 6 H 4 ( B P i n ) 2 : R f = 0 . 0 9 ( h e x a n e s ) . 1 H N M R ( C D C l 3 ) d 1 . 3 3 ( s , 2 4 H , 2 B O 2 C 6 H 1 2 ) , 7 . 7 9 ( s , 4 H ) . M e t h o d 3 : C a t a l y t i c b o r y l a t i o n o f b e n z e n e ( 5 5 m g , 0 . 7 0 m m o l ) w i t h H B P i n ( 2 7 0 m g , 2 . 1 m m o l ) c a t a l y z e d b y C p * R h ( h4 - C 6 M e 6 ) ( 1 5 . 0 m g , 0 . 0 2 5 m m o l ) i n c y c l o h e x a n e ( 1 m L ) a t 1 5 0 C f o r 6 1 h . T h e p r o d u c t r a t i o o f P h B P i n , 1 , 3 - C 6 H 4 ( B P i n ) 2 , 1 , 4 - C 6 H 4 ( B P i n ) 2 a n d 1 , 3 , 5 - C 6 H 3 ( B P i n ) 3 d e t e r m i n e d b y G C - F I D o f t h e c r u d e r e a c t ion mixture, was 3:24:32:41. A dark brown solid (311 mg) was obtained after removal of solvent under vacuum at room temperature. The product ratio of 1,3-C6H4(BPin)2, 1,4-C6H4(BPin)2 and 1,3,5-C6H3(BPin)3 determined by 1H NMR of the crude product was 26:27:43. 1,3,5-C6H3(BPin)3: 1H NMR (CDCl3) d 1 . 3 1 ( s , 3 6 H , 3 B O 2 C 6 H 1 2 ) , 8 . 3 5 ( s , 3 H ) .
5 - ( 4 , 4 , 5 , 5 - T e t r a m e t h y l - 1 , 3 , 2 - d i o x a b o r o l y l ) - 1 , 3 - b i s ( t r i f l u o r o m e t h y l ) b e n z e n e . I n a J . Y o u n g N M R t u b e , b o r y l a t i o n o f 1 , 3 - b i s ( t r i f l u o r o m e t h y l ) b e n z e n e ( 7 5 m g , 0 . 3 5 m m o l ) w i t h H B P i n ( 4 5 m g , 0 . 3 5 m m o l ) i n c y c l o h e x a n e ( 0 . 5 m L ) w a s c a t a l y z e d b y C p * R h ( h4 - C 6 M e 6 ) ( 5 . 0 m g , 0 . 0 1 2 m m o l ) a t 1 5 0 C f o r 1 0 h . 1 , 3 , 5 - C 6 H 3 ( C F 3 ) 2 ( B P i n ) ( 1 0 5 m g , 8 8 % ) w a s i s o l a t e d a s a c o l o r l e s s s o l i d a f t e r c h r o m a t o g r a p h y o n s i l i c a g e l u s i n g C H 2 C l 2 a s t h e e l u e n t . N o o t h e r i s o m e r s w e r e d e t e c t e d b y G C - M S o f t h e c r u d e r e a c t i o n m i x t u r e . 1 H N M R ( C D C l 3 ) d 1 . 3 5 ( s , 1 2 H , B O 2 C 6 H 1 2 ) , 7 . 9 3 ( s , 1 H ) , 8 . 2 2 ( s , 1 H ) . G C - M S ( m / z ) 3 4 0 .
5 - ( 4 , 4 , 5 , 5 - T e t r a m e t h y l - 1 , 3 , 2 - d i o x a b o r o l y l ) - m - x y l e n e ( i s o m e r m i x t u r e ) . 6 I n a J . Y o u n g N M R t u b e , t h e b o r y l a t i o n o f m - x y l e n e ( 7 5 m g , 0 . 7 0 m m o l ) w i t h H B P i n ( 9 0 m g , 0 . 7 0 m m o l ) i n c y c l o h e x a n e ( 0 . 5 m L ) w a s c a t a l y z e d b y C p * R h ( h4 - C 6 M e 6 ) ( 1 0 . 0 m g , 0 . 0 2 5 m m o l ) a t 1 5 0 C f o r 5 9 h . T h e p r o d u c t r a t i o o f 1 , 3 , 5 - C 6 H 3 ( C H 3 ) 2 ( B P i n ) a n d 1 , 3 - C 6 H 3 ( C H 3 ) ( C H 2 B P i n ) , d e t e r m i n e d b y G C - F I D o f t h e c r u d e r e a c t ion mixture, was 94:6. 1,3,5-C6H3(CH3)2(BPin) and 1,3-C6H3(CH3)(CH2BPin) (91 mg, 56%) were isolated as a solid mixture of isomers after chromatography on silica gel using hexanes as the eluent. 1,3,5-C6H3(CH3)2(BPin): Rf = 0.41 (hexanes). 1H NMR (CDCl3) d 1 . 3 3 ( s , 1 2 H , B O 2 C 6 H 1 2 ) , 2 . 3 0 ( s , 6 H , 2 C H 3 ) , 7 . 0 9 ( s , 1 H ) , 7 . 4 2 ( s , 1 H ) . G C - M S ( m / z ) 2 3 2 .
4 - ( 4 , 4 , 5 , 5 - T e t r a m e t h y l - 1 , 3 , 2 - d i o x a b o r o l y l ) v e r a t r o l e . M e t h o d 1 : I n a J . Y o u n g N M R t u b e , t h e b o r y l a t i o n o f v e r a t r o l e ( 9 7 m g , 0 . 7 0 m m o l ) w i t h H B P i n ( 9 0 m g , 0 . 7 0 m m o l ) w a s c a t a l y z e d b y C p * R h ( h4 - C 6 M e 6 ) ( 5 . 0 m g , 0 . 0 1 2 m m o l ) i n c y c l o h e x a n e ( 0 . 5 m L ) a t 1 5 0 C f o r 3 7 h . T h e p r o d u c t r a t i o o f 1 , 2 , 4 - C 6 H 3 ( O C H 3 ) 2 ( B P i n ) t o a n u n i d e n t i f i e d m o n o - b o r y l a t e d p r o d u c t , d e t e r m i n e d b y G C - F I D o f t h e c r u d e r e a c t i o n m i x t u r e , w a s 9 8 : 2 . 1,2,4-C6H3(OCH3)2(BPin) (118 mg, 64%) was isolated as a colorless solid after chromatography on silica gel using a hexanes-ethyl acetate eluent gradient from 20:1 to 10:1. 1,2,4-C6H3(OCH3)2(BPin): mp 74-77 C. Rf = 0.23 (hexanes:ethyl acetate = 9:1). 1H NMR (CDCl3) d 1 . 3 2 ( s , 1 2 H , B O 2 C 6 H 1 2 ) , 3 . 8 8 ( s , 3 H , O C H 3 ) , 3 . 9 0 ( s , 3 H , O C H 3 ) , 6 . 8 6 ( d , J = 8 . 0 H z , 1 H ) , 7 . 2 6 ( d , J = 1 . 5 H z , 1 H ) , 7 . 4 0 ( d d , J = 8 . 0 , 1 . 5 H z , 1 H ) . 1 3 C N M R ( C D C l 3 ) d 2 4 . 8 2 , 5 5 . 7 1 , 5 5 . 8 1 , 8 3 . 6 3 , 1 1 0 . 4 2 , 1 1 6 . 4 6 , 1 2 8 . 5 2 , 1 4 8 . 2 8 , 1 5 1 . 5 9 . 1 1 B N M R ( C D C l 3 ) d 3 0 . 3 . E l e m e n t a l a n a l y s i s f o r C 1 4 H 2 1 B O 4 c a l c d . C ( 6 3 . 6 6 % ) , H ( 8 . 0 1 % ) , N ( 0 . 0 0 % ) . F o u n d C ( 6 3 . 4 1 % ) , H ( 8 . 1 8 % ) , N ( 0 . 0 1 % ) . G C - M S ( m / z ) 2 6 4 . M e t h o d 2 : I n a n a i r - f r e e f l a s k , t h e b o r y l a t i o n o f v e r a t r o l e ( 9 7 m g , 0 . 7 0 m m o l ) w i t h H B P i n ( 2 7 0 m g , 2 . 1 m m o l ) w a s c a t a l y z e d b y C p * R h ( h4 - C 6 M e 6 ) ( 1 0 . 0 m g , 0 . 0 2 5 m m o l ) i n c y c l o h e x a n e ( 1 m L ) a t 1 5 0 C f o r 4 5 h . T h e p r o d u c t r a t i o o f 1 , 2 , 4 - C 6 H 3 ( O C H 3 ) 2 ( B P i n ) t o a n u n i d e n t i f i e d m o n o - b o r y l a t e d p r o d u c t , d e t e r m i n e d b y G C - F I D o f t h e c r u d e r e a c t i o n m i x t u r e , w a s 9 9 : 1 . 1 , 2 , 4 - C6H3(OCH3)2(BPin) (153 mg, 82%) was isolated as a colorless solid.
5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolyl)-3-methylanisole. In an air-free flask, the borylation of 3-methylanisole (86 mg, 0.70 mmol) with HBPin (113 mg, 0.88 mmol) was catalyzed by Cp*Rh( h4 - C 6 M e 6 ) ( 1 5 . 0 m g , 0 . 0 3 7 m m o l ) i n c y c l o h e x a n e ( 1 m L ) a t 1 5 0 C f o r 2 5 h . T h e p r o d u c t r a t i o o f 1 , 3 , 5 - C 6 H 3 ( C H 3 ) ( O C H 3 ) ( B P i n ) t o o t h e r u n i d e n t i f i e d m o n o - b o r y l a t e d p r o d u c t s , d e t e r m i n e d b y G C - F I D o f t h e c r u d e r e a c t i o n m i x t u r e , w a s 9 2 : 5 : 3 . 1 , 3 , 5 - C 6 H 3 ( O C H 3 ) ( C H 3 )(BPin) (93 mg, 54%) was isolated as a colorless solid after chromatography on silica gel using hexanes to hexanes:ethyl acetate (20:1) as the gradient eluent. 1,3,5-C6H3(OCH3)(CH3)(BPin): mp 55-56 C. Rf = 0.52 (hexanes:ethyl acetate = 20:1). 1H NMR (CDCl3) d 1 . 3 3 ( s , 1 2 H , B O 2 C 6 H 1 2 ) , 2 . 3 1 ( s , 3 H , C H 3 ) , 3 . 8 0 ( s , 3 H , O C H 3 ) , 6 . 8 2 ( m , 1 H ) , 7 . 1 1 ( d , J = 2 . 5 H z , 1 H ) , 7 . 2 2 ( m , 1 H ) . 1 3 C N M R ( C D C l 3 ) d 2 1 . 2 1 , 2 4 . 8 3 , 5 5 . 2 3 , 8 3 . 7 6 , 1 1 5 . 4 8 , 1 1 8 . 7 9 , 1 2 8 . 0 1 , 1 3 8 . 9 1 , 1 5 9 . 1 3 . 1 1 B N M R ( C D C l 3 ) d 3 0 . 9 . E l e m e n t a l a n a l y s i s for C14H21BO3 calcd. C (67.77%), H (8.53%), N (0.00%). Found C (67.54%), H (8.53%), N (0.02%). GC-MS (m/z) 248.
5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolyl)-m-N,N-dimethylanisidine. In an air-free flask, the borylation of m-N,N-dimethylanisidine2 (90 mg, 0.60 mmol) with HBPin (305 mg, 2.38 mmol) was catalyzed by Cp*Rh( h4 - C 6 M e 6 ) ( 1 0 . 0 m g , 0 . 0 2 5 m m o l ) i n c y c l o h e x a n e ( 1 m L ) a t 1 5 0 C f o r 1 9 h . T h e p r o d u c t r a t i o o f 1 , 3 , 5 - C 6 H 3 ( O C H 3 ) ( N M e 2 ) ( B P i n ) t o a n o t h e r u n i d e n t i f i e d m o n o - b o r y l a t e d p r o d u c t , d e t e r m i n e d b y G C - F I D o f t h e c r u d e r e a c t i o n m i x t u r e , w a s 9 5 : 5 . 1 , 3 , 5 - C 6 H 3 ( O C H 3 ) ( N M e 2 ) ( B P i n ) ( 1 2 4 m g , 7 5 % ) w a s i s o l a t e d a s a c o l o r l e s s s o l i d a f t e r s u b l i m a t i o n ( 0 . 0 3 m m H g , 8 0 C ) . 1 , 3 , 5 - C 6 H 3 ( O C H 3 ) ( N M e 2 ) ( B P i n ) : m p 6 4 - 6 6 C . R f = 0 . 3 3 ( h e x a n e s : e t h y l a c e t a t e = 9 : 1 ) . 1 H N M R ( C D C l 3 ) d 1 . 3 2 ( s , 1 2 H , B O 2 C 6 H 1 2 ) , 2 . 9 3 ( s , 6 H , N M e 2 ) , 3 . 8 1 ( s , 3 H , O C H 3 ) , 6 . 3 7 ( u n r e s o l v e d d d , 1 H ) , 6 . 7 0 ( d , J = 2 . 2 H z , 1 H ) , 6 . 8 2 ( d , J = 2 . 5 H z , 1 H ) . 1 3 C N M R ( C D C l 3 ) d 2 4 . 8 1 , 4 0 . 7 2 , 5 5 . 2 6 , 8 3 . 6 5 , 1 0 2 . 9 0 , 1 0 6 . 2 2 , 1 1 2 . 2 7 , 1 5 1 . 5 9 , 1 6 0 . 1 4 . 1 1 B N M R ( C D C l 3 ) d 3 0 . 8 . E l e m e n t a l a n a l y s i s f o r C 1 5 H 2 4 B N O 3 c a l c d . C ( 6 5 . 0 0 %), H (8.73%), N (5.05%). Found C (65.25%), H (8.98%), N (4.86%). GC-MS (m/z) 277.
5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolyl)-1,3-N,N,N,N-tetramethyl-phenylenediamine. In an air-free flask, the borylation of 1,3-N,N,N,N-tetramethylphenylenediamine3 (115 mg, 0.70 mmol) with HBPin (269 mg, 2.10 mmol) was catalyzed by Cp*Rh( h4 - C 6 M e 6 ) ( 1 5 . 0 m g , 0 . 0 3 7 m m o l ) i n c y c l o h e x a n e ( 1 m L ) a t 1 5 0 C f o r 2 8 h . T h e p r o d u c t r a t i o o f 1 , 3 , 5 - C 6 H 3 ( N M e 2 ) 2 ( B P i n ) t o a n o t h e r u n i d e n t i f i e d m o n o - b o r y l a t e d p r o d u c t , d e t e r m i n e d b y G C - F I D o f t h e c r u d e r e a c t i o n m i x t u r e , w a s 9 7 : 3 . 1 , 3 , 5 - C 6 H 3 ( N M e 2 ) 2 ( B P i n ) ( 1 4 0 m g , 6 9 % ) w a s i s o l a t e d a s a c o l o r l e s s s o l i d a f t e r r e c r y s t a l l i z a t i o n f r o m h o t c y c l o h e x a n e . 1 , 3 , 5 - C 6 H 3 ( N M e 2 ) 2 ( B P i n ) : m p 1 7 8 - 1 8 0 C . R f = 0 . 2 2 ( h e x a n e s : e t h y l a c e t a t e = 5 : 1 ) . 1 H N M R ( C D C l 3 ) d 1 . 3 2 ( s , 1 2 H , B O 2 C 6 H 1 2 ) , 2 . 9 4 ( s , 1 2 H , 2 N M e 2 ) , 3 . 8 1 ( s , 3 H , O C H 3 ) , 6 . 2 3 ( t , J = 2 . 2 H z , 1 H ) , 6 . 6 5 ( d , J = 2 . 2 H z , 2 H ) . 1 3 C N M R ( C D C l 3 ) d 2 4 . 8 1 , 4 1 . 0 5 , 8 3 . 4 3 , 1 0 1 . 3 0 , 1 0 8 . 7 7 , 1 5 1 . 3 8 . 1 1 B N M R ( C D C l 3 ) d 3 1 . 0 . H R M S f o r C 1 6 H 2 7 B N 2 O 2 c a l c d . 2 9 0 . 2 1 6 9 , f o u n d 2 9 0 . 2 1 6 7 . G C - M S ( m / z ) 2 9 0 .
3 - ( 4 , 4 , 5 , 5 - T e t r a m e t h y l - 1 , 3 , 2 - d i o x a b o r o l y l ) - N - t r i - i s o - p r o p y l s i l y l p y r r o l e . I n a n a i r - f r e e f l a s k , t h e b o r y l a t i o n o f N - t r i - i s o - p r o p y l s i l y l p y r r o l e 4 ( 1 5 6 m g , 0 . 7 0 m m o l ) w i t h H B P i n ( 2 6 9 m g , 2 . 1 0 m m o l ) w a s c a t a l y z e d b y C p * R h ( h4 - C 6 M e 6 ) ( 1 0 . 0 m g , 0 . 0 2 5 m m o l ) i n c y c l o h e x a n e ( 1 m L ) a t 1 5 0 C f o r 4 1 h. The product ratio of N-iPr3Si-pyrrole-3-BPin to an unidentified mono-borylated product, determined by GC-FID of the crude reaction mixture, was 99:1. N-iPr3Si-pyrrole-3-BPin (199 mg, 81%) was isolated as colorless oil after chromatography on silica gel using hexanes to hexanes:ethyl acetate (20:1) as the gradient eluent. . N-iPr3Si-pyrrole-3-BPin: Rf = 0.43 (hexanes:ethyl acetate = 20:1). 1H NMR (CDCl3) d 1 . 0 6 ( d , J = 7 . 3 H z , 1 8 H , 6 C H 3 ) , 1 . 3 0 ( s , 1 2 H , B O 2 C 6 H 1 2 ) , 1 . 4 4 ( s e p t e t , J = 7 . 3 H z , 3 H , 3 C H ) , 6 . 6 0 ( d d , J = 2 . 7 , 1 . 2 H z , 1 H ) , 6 . 7 9 ( d d , J = 2 . 7 , 2 . 0 H z , 1 H ) , 7 . 2 1 - 7 . 2 2 ( u n r e s o l v e d d d , 1 H ) . 1 3 C N M R ( C D C l 3 ) d 1 1 . 6 2 , 1 7 . 7 8 , 2 4 . 8 4 , 8 2 . 6 9 , 1 1 5 . 5 7 , 1 2 4 . 9 6 , 1 3 3 . 6 5 . 1 1 B N M R ( C D C l 3 ) d 3 0 . 5 . H R M S f o r C 1 6 H 2 7 B N 2 O 2 c a l c d . 3 4 9 . 2 6 1 2 , f o u n d 3 4 9 . 2 6 0 2 . G C - M S ( m / z ) 2 9 0 .
B o r y l a t i o n o f 1 , 3 - d i c h l o r o b e n z e n e : I n a J . Y o u n g N M R t u b e , t h e b o r y l a t i o n o f 1 , 3 - d i c h l o r o b e n z e n e ( 1 0 3 m g , 0 . 7 0 m m o l ) w i t h H B P i n ( 9 0 m g , 0 . 7 0 m m o l ) w a s c a t a l y z e d b y C p * R h ( h4 - C 6 M e 6 ) ( 5 . 0 m g , 0 . 0 1 2 m m o l ) i n c y c l o h e x a n e ( 0 . 5 m L ) a t 1 5 0 C f o r 7 h . A m i x t u r e o f b o r y l a t i o n a n d r e d u c t i o n p r o d u c t s w a s o b t a i n e d a s d e t e r m i n e d b y G C - M S o f t h e c r u d e r e a c t i o n m i x t u r e . T h e p r o d u c t r a t i o o f c h l o r o b e n z e n e , u n r e a cted 1,3-dichlorobenzene, PhBPin, ClC6H4(BPin), 1,3-Cl2C6H4(BPin) and ClC6H3(BPin)2, determined by GC-FID of the crude reaction mixture, was 19:30:2:14:31:5.
Bowyer, W. J.; Merkert, J. W.; and Geiger, W. E. Organometallics, 1989, 8, 191-198.
Giumanini, A. G.; Chiavari, G.; Musiani, M. M.; Rossi, P. Synth. 1980, 743-746.
Torf, S. F.; Khromov-Borisov, N. V. Zhur. Obshchei Khim. 1960, 30, 1798-1805.
Bray, B. L.; Mathies, P. H.; Naef, R.; Solas, D. R.; Tidwell, T. T.; Artis, D. R.; Muchowski, J. M. J. Org. Chem. 1990, 55, 6317-6328.
Murata, M.; Oyama, T.; Watanabe, S.; Masuda, Y. J. Org. Chem. 2000, 65, 164-168.
Cho, J.-Y.; Iverson, C. N.; Smith, M. R., III. J. Am. Chem. Soc. 2000, 122, 12868-12869.
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