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XH , 6! 6! l o$ 0 $ 6! ]( ^ ]( 6! ( Synthesis of Diynes and Tetraynes from in situ Desilylation/Dimerization of Acetylenes:
Matthew A. Heuft, Shawn K. Collins, Glenn P. A. Yap, and Alex G. Fallis*
Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario, Canada, K5N 6N5
afallis@science.ottawa.ca
Supplementary Information & Experimental.
General. Proton magnetic resonance and carbon magnetic resonance spectra (1H NMR) were measured at 500 MHz with a Bruker AMX500 or at 200 MHz with a Varian Gemini spectrometer. Chemical s h i f t s a r e r e p o r t e d i n p a r t s p e r m i l l i o n ( p p m ) d o w n f i e l d f r o m t e t r a m e t h y l s i l a n e ( s c a l e ) . T h e m u l t i p l i c i t y ( s = s i n g l e t , d = d o u b l e t , t = t r i p l e t , q = q u a r t e t , b r = b r o a d ) , n u m b e r o f p r o t o n s a n d c o u p l i n g c o n s t a n t s ( r e p o r t e d i n H z ) a r e i n d i c a t e d i n p a r e n t h e s e s . E l e c t r o n i m p a c t m a s s s p e c t r a E I ( M S ) w e r e d e t e r m i n e d o n a K r a t o s C o n c e p t 2 H i n s t r u m e n t u s i n g a n i o n i z a t i o n e n e r g y o f 7 0 e V . E l e c t r o s p r a y m a s s s p e c t r a E S ( M S ) w e r e d e t e r m i n e d o n a M i c r o m a s s Q u a t t r o L C w i t h a p u m p r a t e o f 2 0 mL / m i n . E l e m e n t a l a n a l yses were performed at M-H-W Laboratories, Phoenix, Arizona, USA. The purity of all title compounds was judged to be > 95 % as determined by a combination of GC-MS, 1H NMR and 13C NMR analyses.
In the preparation of TIPS-protected acetylenic precursors, all non-aqueous reactions were performed under an atmosphere of dry nitrogen or dry argon in flame or oven dried glassware equipped with a magnetic stir bar and a rubber septum. Standard inert atmosphere techniques were used in handling all air and moisture sensitive reagents. Reactions were monitored by analytical thin layer chromatography (TLC) using commercial aluminum sheets pre-coated (0.2 mm layer thickness) with silica gel 60 F254 (E. Merck). Product purification by conventional and flash column chromatography was performed using E. Merck Silica Gel (70-230 or 230-400 mesh). Petroleum ether refers to a mixture of hydrocarbons with a boiling range of 30 60 C. Anhydrous diethyl ether (ether), anhydrous tetrahydrofuran (THF) were freshly distilled from benzophenone/sodium. Dry benzene, toluene, dimethylformamide (DMF), dichloromethane, and triethylamine were distilled from NaH or CaH. Cu(OAc)2 was prepared from the dihydrate Cu(OAc)22H2O by refluxing in acetic anhydride for 15 h prior to use. All commercial starting materials were purchase from Aldrich Chemical Company unless otherwise stated.
Standard Desilylation/Oxidative Dimerization Method Using Cu(OAc)2
A solution of tetra-n-butylammonium fluoride (1.0 M in THF, 1 eq) in THF (5 mL) was added over 2 h via syringe pump to a stirred solution of Cu(OAc)2 (3 eq) and corresponding TIPS-acetylene (1 eq) in pyridine/ether (3:1) (substrate concentration was 3.3 mM). The blue solution became emerald green once addition began. Once addition was complete, the solution was poured into ether and HCl (1 M). The organic phase was washed excessively with HCl (1 M) until all pyridine was removed and the organic phase was dried and concentrated to yield a crude solid. The solid was further purified by chromatography (petroleum ether unless otherwise specified) to yield the dimer product.
Standard Desilylation/Oxidative Dimerization Method Using CuCl/TMEDA
A solution of tetra-n-butylammonium fluoride (1.0 M in THF, 1 eq) in THF (5 mL) was added over 2 h via syringe pump to a solution of CuCl (3 eq), TMEDA (100 eq) and corresponding TIPS-acetylene (1 eq) in benzene (substrate concentration was 3.3 mM). The lime-green solution became emerald green after addition began. Once addition was complete, the solution was poured into ether and HCl (1 M). The organic phase was washed to remove TMEDA and the organic phase was dried and concentrated to yield a crude solid. The solid was further purified by chromatography (petroleum ether unless otherwise specified) to yield the dimer product.
Triisopropyl-(4-phenyl-buta-1,3-diynyl)-silane (1b)
nBuLi (2.27 M, 15.8 mL, 35.8 mmol) was added to a solution of 3 (4.34 g, 17.9 mmol) in THF (40 mL) at 78 C and the resulting deep yellow solution was stirred for 5 min. A solution of ZnBr2 (4.12 g, 18.3 mmol) in THF (40 mL) at 22 C was transferred by canula to the solution and warmed to 22 C and stirred for 15 min. A solution of Pd(PPh3)4 (500 mg, 5 mol %) and iodobenzene (1.0 mL, 8.94 mmol) was transferred by canula to the solution which was then heated to reflux overnight (~18 h). The reaction mixture was then quenched by the addition of silica gel. Concentration and dry packed chromatography give the product as a yellow oil (1.61 g, 64 %); 1H NMR (500 MHz, CDCl3 ) 7 . 5 0 ( d d , J = 8 . 2 , 1 . 3 H z , 2 H ) , 7 . 3 7 7 . 2 9 ( m , 3 H ) , 1 . 1 3 ( s , 2 1 H ) ; 1 3 C N M R ( 1 2 5 M H z , C D C l 3 ) 1 3 2 . 6 ( d ) , 1 2 9 . 2 ( d ) , 1 2 8 . 3 ( d ) , 1 2 1 . 5 ( s ) , 8 9 . 6 ( s ) , 8 7 . 8 ( s ) , 7 5 . 5 ( s ) , 7 4 . 7 ( s ) , 1 8 . 5 ( q ) , 1 1 . 3 ( d ) ; M S ( E I ) m / z 2 8 2 ( M + ) , 2 3 9 , 2 1 1 , 1 8 3 , 1 6 9 ; H R M S c a l c ' d for C19H26Si 282.1804 (M+), found 282.1787.
[4-(2-Bromophenyl)-buta-1,3-diynyl]-triisopropyl-silane (1d)
nBuLi (36.4 mL, 82.6 mmol) was added to a solution of 32 (10 g, 41.3 mmol) in THF (60 mL) at 0 C and the resulting deep yellow solution was stirred for 5 min. A solution of ZnBr2 (9.3 mg, 41.3 mmol) in THF (20 mL) at 22 C was transferred by canula to the solution and warmed to 22 C and stirred for 15 min. A solution of Pd(PPh3)4 (600 mg, 0.52 mmol) and 1-bromo-2-iodobenzene (7.8 g, 27.5 mmol) was then transferred by canula to the reaction mixture and heated to reflux overnight (~15 h). The reaction was then quenched by the addition of silica gel. Concentration and dry packed chromatography give the product as a clear liquid (3.05 g, 35 %); 1H NMR (200 MHz, CDCl3) d 7 . 5 4 ( m , 2 H ) , 7 . 2 2 ( m , 2 H ) , 1 . 1 1 ( s , 2 1 H ) ; 1 3 C N M R ( 5 0 M H z , C D C l 3 ) d 1 3 4 . 7 ( d ) , 1 3 2 . 5 ( d ) , 1 3 0 . 1 ( d ) , 1 2 6 . 9 ( s ) , 1 2 6 . 2 ( s ) , 1 2 4 . 1 ( s ) , 8 9 . 8 ( d ) , 8 9 . 2 ( d ) , 7 9 . 5 ( s ) , 7 3 . 5 ( s ) , 1 8 . 5 ( q ) , 1 1 . 3 ( d ) ; M S ( E I ) m / z 3 6 0 ( M + ) , 3 2 0 , 3 1 9 , 3 1 7 , 2 9 1 , 2 8 9 , 2 7 7 , 2 7 5 , 263, 261, 209, 153; HRMS calc'd for C19H25BrSi 360.0910 (M+), found 360.0922; Anal calc'd for C19H25BrSi: C 63.15, H 6.98, found C 62.95, H 6.91.
[4-(3-Dibutylamino-phenyl)-buta-1,3-diynyl]-triisopropyl-silane (1e)
A solution of nBuLi (2.04 M, 22.4 mL, 45.6 mmol) was added to a 78 C solution of 32 (5.50 g, 22.7 mmol) in THF (150 mL). The resulting pale yellow colored solution was stirred for 2 min followed by the addition of a solution of ZnBr2 (5.27 g, 23.4 mmol, 1.55 eq) in THF (100 mL). The colourless solution was stirred at 78 C for 5 min then warmed to 0 C for 15 min. A mixture of N,N-dibutyl-3-iodoaniline (5.00g, 15.1 mmol, 1 eq), Pd(PPh3)4 (1.75 g, 10 mol %) in THF (150 mL) was added by canula and the reaction was heated to reflux for 18 h. Once cooled to 22 C, silica gel was added to the reaction flask and its contents were concentrated to dryness. After chromatography (petroleum ether / CH2Cl2, 20:1), the product was isolated as a yellow oil (4.70 g, 76 %); 1H NMR (500 MHz, CDCl3 ) 7 . 1 1 ( t , J = 7 . 9 H z , 1 H ) , 6 . 7 9 6 . 7 6 ( m , 3 H ) , 3 . 2 4 ( t , J = 7 . 7 H z , 4 H ) , 1 . 5 9 1 . 5 2 ( m , 4 H ) , 1 . 4 0 1 . 3 0 ( m , 4 H ) , 1 . 1 4 ( s , 2 1 H ) , 0 . 9 7 ( t , J = 7 . 3 H z , 6 H ) ; 1 3 C N M R ( 1 2 5 M H z , C D C l 3 ) 1 4 7 . 9 ( s ) , 1 2 9 . 1 ( d ) , 1 2 1 . 9 ( s ) , 1 1 9 . 7 ( d ) , 1 1 5 . 3 ( d ) , 1 1 3 . 0 ( d ) , 9 0 . 0 (s), 86.7 (s), 73.3 (s), 65.8 (s), 50.7 (t), 29.0 (t), 20.4 (t), 18.4 (q), 13.9 (q), 11.3 (d); MS (EI) m/z 409 (M+), 319, 221, 163, 135; HRMS calc'd for C27H43NSi 409.3165 (M+), found 409.3157; Anal. calc'd for C27H43NSi: C 79.15, H 10.58, found C 78.95, H 10.68.
Triisopropyl-(4-naphthalen-1-yl-buta-1,3-diynyl)-silane (1f)
nBuLi (1.45 mL , 2 . 2 8 M , 3 . 3 0 m m o l ) w a s a d d e d t o a s o l u t i o n o f 3 2 ( 4 0 0 m g , 1 . 6 5 m m o l ) i n T H F ( 1 5 m L ) a t 0 C a n d t h e r e s u l t i n g d e e p y e l l o w s o l u t i o n w a s s t i r r e d f o r 5 m i n . A s o l u t i o n o f Z n B r 2 ( 3 4 0 m g , 1 . 6 5 m m o l ) i n T H F ( 8 m L ) a t 2 2 C w a s t r a n s f e r r e d b y c a n u l a t o t h e s olution and warmed to 22 C and allowed to stir for 15 min. A solution of Pd(PPh3)4 (50 mg, 0.04 mmol) and 1-bromonaphthalene (310 mg, 1.50 mmol) was then transferred by canula to the solution and heated to reflux overnight (~15 h). The reaction mixture was then quenched by the addition of silica gel. Concentration and dry packed chromatography gave the product as a pale yellow solid (350 mg, 64 %); 1H NMR (200 MHz, CDCl3) d 8 . 3 8 ( d , J = 7 . 9 , 1 H ) , 7 . 8 0 ( m , 2 H ) , 7 . 3 7 - 7 . 6 3 ( m , 4 H ) , 1 . 2 0 ( s , 2 1 H ) ; 1 3 C N M R ( 5 0 M H z , C D C l 3 ) d 1 3 4 . 0 ( s ) 1 3 3 . 0 ( s ) , 1 3 2 . 3 ( d ) , 1 2 9 . 7 ( d ) , 1 2 8 . 4 ( d ) , 1 2 7 . 1 ( d ) , 1 2 6 . 6 ( d ) , 1 2 6 . 0 ( d ) , 1 2 5 . 1 ( d ) , 1 1 9 . 1 ( s ) , 8 9 . 7 ( s ) , 8 8 . 9 ( s ) , 7 9 . 3 ( s ) , 7 3 . 9 ( s ) , 1 8 . 6 ( q ) , 11.3 (d); MS (EI) m/z 332 (M+), 289, 247, 219, 203, 184, 141, 115, 44; HRMS calc'd for C23H28Si 332.1961 (M+), found 332.1955.
Triisopropyl-octa-1,3-diynyl-silane (1g)
1-Hexyne (500 mg, 6.09 mmol), Pd2(dba)3 (70 mg, 0.76 mmol), CuI (20 mg, 0.11 mmol), 1,2,2,6,6-pentamethylpiperidine (1.37 mL, 7.6 mmol) and 1-bromo-2-(triisopropylsilyl)acetylene (1.0 g, 0.38 mmol) were combined in benzene (10 mL) at 22 C. The solution was stirred for 19 h. The reaction mixture was quenched by the addition of silica gel. C o n c e n t r a t i o n a n d d r y p a c k e d c h r o m a t o g r a p h y g a v e t h e p r o d u c t a s a p a l e y e l l o w l i q u i d ( 4 3 3 m g , 4 3 % ) ; 1 H N M R ( 2 0 0 M H z , C D C l 3 ) d 2 . 2 5 ( t , J = 6 . 7 , 2 H ) 1 . 4 8 ( m , 2 H ) , 1 . 0 5 ( s , 2 1 H ) , 1 . 0 5 ( m , 2 H ) , 0 . 8 8 ( t , J = 6 . 8 , 3 H ) ; 1 3 C N M R ( C D C l 3 , 5 0 M H z ) d 9 0 . 1 ( s ) , 7 9 .7 (s), 78.7 (s), 65.7 (s), 30.1 (t), 21.9 (t), 18.9 (q), 18.4 (q), 13.5 (t), 11.2 (d); MS (EI) m/z 262 (M+), 219, 191, 177, 163, 149, 111, 97, 83, 69, 44; HRMS calc'd for C17H30Si 262.2118 (M+), found 262.2126.
Triisopropyl-(4-thiophen-2-yl-buta-1,3-diynyl)-silane (1h)
nBuLi (2.06 mL, 3.3 mmol) was added to a solution of 32 (400 mg, 1.65 mmol) in THF (15 mL) at 0 C and the resulting deep yellow solution was stirred for 5 min. A solution of ZnBr2 (375 mg, 1.65 mmol) in THF (10 mL) at 22 C was transferred b y c a n u l a t o t h e s o l u t i o n a n d w a r m e d t o 2 2 C a n d a l l o w e d t o s t i r f o r 1 5 m i n . A s o l u t i o n o f P d ( P P h 3 ) 4 ( 5 0 m g , 0 . 0 4 m m o l ) a n d 2 - b r o m o t h i o p h e n e ( 1 1 0 mL , 1 . 1 4 m m o l ) w a s t h e n t r a n s f e r r e d b y c a n u l a t o t h e s o l u t i o n a n d h e a t e d t o r e f l u x o v e r n i g h t ( ~ 1 5 h ) . T h e r e a c t i o n m i x t u r e w a s t h e n q u e n c h e d b y t h e a d d i t i o n o f s i l i c a g e l . C o n c e n t r a t i o n a n d d r y p a c k e d c h r o m a t o g r a p h y g a v e t h e p r o d u c t a s a y e l l o w o i l ( 2 8 4 m g , 8 6 % ) ; 1 H N M R ( 2 0 0 M H z , C D C l 3 ) d 7 . 2 7 ( m , 2 H ) , 6 . 9 3 ( m , 1 H ) , 1 . 1 0 ( s , 2 1 H ) ; 1 3 C N M R ( 5 0 M H z , C D C l 3 ) d 134.5 (d), 128.6 (d), 127.0 (d), 121.7 (s), 90.2 (s), 89.2 (s), 78.7 (s), 68.6 (s), 18.5 (q), 11.2 (d); MS (EI) m/z 288 (M+), 245, 217, 189, 165, 135, 94, 59; HRMS calc'd for C17H24SSi 288.1361 (M+), found 288.1368.
(6-Anthracen-9-yl-hexa-1,3,5-triynyl)-triisopropyl-silane (1i)
The triyne (6-anthracen-9-yl-hexa-1,3,5-triynyl)-triisopropyl-silane was constructed in a parallel manner to the methods described by Tykwinski (see Supplemental Scheme 1).
EMBED ChemDraw.Document.5.0
Supplemental Scheme 1: Synthetic scheme for the preparation of 1i.
Step 1: 4-Bromoanthracene (I) (1.5 g, 5.83 mmol), Pd(PPh3)2Cl2 (100 mg, 0.14 mmol), Et3N (30 mL), and CuI (50, mg, 0.26 mmol) were combined in THF (30 mL). The solution was degassed by passing a stream of argon gas through the solution for 10 min. TMS-acetylene was then added (905 uL, 6.42 mmol) and the mixture heated at reflux for 15 h. The reaction mixture was cooled to 22 C and quenched by the addition of silica gel. Concentration and dry packed chromatography (petroleum ether) give anthracen-9-ylethynyl-trimethylsilane (II) as a yellow solid (1.58 g, 100 %). The silylacetylene was carried on directly to the next step.
Step 2: Compound II (890 mg, 3.24 mmol) and K2CO3 (excess) were combined in THF (15 mL) and MeOH (15 mL). The mixture was vigorously stirred for 8 h and poured into a mixture of ether and water. The organic phase was dried (MgSO4) and concentrated and the crude solid was passed through a silica gel plug (petroleum ether) to yield 9-ethynyl-anthracene (III) as a yellow solid (650 mg, 99 %). The acetylene was carried on directly to the next step.
Step 3: nBuLi (1.35 mL, 2.27 M, 3.04 mmol) was added to a >
Transfer interrupted!
(590 mg, 2.92 mmol) in THF (20 mL) and was cooled to 78 oC and stirred for 15 min. A bright yellow solution resulted. The reaction was quenched by the addition of p-formaldehyde (262 mg, 2.91 mmol) in THF (20 mL) and stirred at 22 C for 15 h. The mixture was partitioned between ether and water . T h e o r g a n i c p h a s e w a s d r i e d ( M g S O 4 ) , c o n c e n t r a t e d , a n d c h r o m a t o g r a p h e d ( p e t r o l e u m e t h e r / e t h e r , 5 : 1 ) t o y i e l d 3 - a n t h r a c e n - 9 - y l - p r o p - 2 - y n - 1 - o l ( I V ) a s a y e l l o w - b r o w n s o l i d ( 6 0 0 m g , 8 9 % ) ; 1 H N M R ( 2 0 0 M H z , C D C l 3 ) d 8 . 5 0 ( d , J = 8 . 9 , 2 H ) , 8 . 4 0 ( s , J = 7 . 8 H z , 1 H ) , 7 . 9 7 ( d , J = 7 . 8 H z , 2 H ) , 7 . 5 4 ( m , 4 H ) , 4 . 8 1 ( s , 2 H ) , 2 . 0 3 ( b r s , 1 H ) ; 1 3 C N M R ( 5 0 M H z , C D C l 3 ) d 1 3 2 . 7 ( s ) , 1 3 0 . 9 ( s ) , 1 2 8 . 6 ( d ) , 1 2 7 . 9 ( d ) , 1 2 6 . 6 ( d ) , 1 2 6 . 5 ( d ) , 1 2 5 . 6 ( d ) , 1 0 8 . 6 ( s ) , 9 8 . 3 ( s ) , 8 2 . 3 ( s ) , 5 2 . 1 ( t ) ; M S ( E I ) m / z 2 3 2 ( M + ) , 2 0 2 , 1 7 8 , 1 43, 101, 44, 29; HRMS calc'd for C17H12O 232.0887 (M+), found 232.0896.
Step 4: The alcohol was then oxidized in the following manner. BaMnO4 (2.8 g, 10.9 mmol) was added to a solution of 3-anthracen-9-yl-prop-2-yn-1-ol (IV) (490 mg, 2.11 mmol) in methylene chloride (15 mL) and the mixture was stirred for 4 h. The mixture was then filtered through a pad of CeliteTM and the filtrate was concentrated to yield anthracen-9-yl-propynal (V) as a yellow solid (482 mg, 99 %), which was carried on directly to the next step.
Step 5: Alkylation was achieved as follows. nBuLi (1.7 mL, 2.27 M, 3.86 mmol) was added to a 0 C solution of TIPS-acetylene (875 uL, 3.91 mmol) in THF (10mL) and was stirred at 0 oC for 1 h. Anthracen-9-yl-propynal (V) (600 mg, 2.61 mmol) was added and the reaction mixture was to warmed to 22 oC and stirred for 15 h. The mixture was partitioned between ether and water. The organic phase was dried (MgSO4), concentrated, chromatographed (petroleum ether/ ether, 5:1) to yield 1-anthracen-9-yl-5-triisopropylsilanyl-penta-1,4-diyn-3-ol (VI) as an orange oil (415 mg, 39 %). Alcohol VI was carried on directly to the next step.
Step 6: Alcohol VI (415 mg, 1.01 mmol) was immediately added to a mixture of PCC (260 mg, 1.20 mmol), CeliteTM (400 mg) in methylene chloride (15 mL) and stirred at 22 oC for 5 h. The mixture was then filtered through a pad of CeliteTM and the filtrate evaporated to yield 1-anthracen-9-yl-5-triisopropylsilanyl-penta-1,4-diyn-3-one (VII) as a yellow oil (200 mg, 48 %); 1H N M R ( 2 0 0 M H z , C D C l 3 ) d 8 . 4 0 ( d , J = 8 . 2 H z , 2 H ) , 8 . 3 8 ( s , 1 H ) , 7 . 8 9 ( d , J = 8 . 4 H z , 2 H ) , 7 . 4 7 ( m , 4 H ) , 1 . 2 0 ( s , 2 1 H ) ; 1 3 C N M R ( 5 0 M H z , C D C l 3 ) d 1 5 9 . 9 ( s ) , 1 3 4 . 5 ( s ) , 1 3 2 . 0 ( d ) , 1 3 0 . 6 ( s ) , 1 2 8 . 9 ( d ) , 1 2 8 . 0 ( d ) , 1 2 6 . 0 ( d ) , 1 2 5 . 8 ( d ) , 1 1 2 . 1 ( s ) . 1 0 5 . 5 ( s ) , 1 00.9 (s), 97.1 (s), 89.7 (s); MS (EI) m/z 410 (M+), 382, 339, 297, 269, 229, 208, 180, 143, 79, 61, 44; HRMS calc'd for C28H30OSi 410.2067 (M+), found 410.2052.
Step 7: Ketone VII (170 mg, 0.41 mmol), CBr4 (194 mg, 0.59 mmol), and PPh3 (333 mg, 1.26 mmol) were combined in methylene chloride (40 mL) and stirred for 15 h. Pentane was then added to the mixture and a white precipitate formed (Ph3P=O). The mixture was filtered and the filtrate evaporated to yield a yellow oil. This oil was dissolved in a minimum amount of methylene chloride and diluted with pentane to precipitate any remaining triphenylphosphine oxide. This sequence was repeated until the addition of pentane produced no visible precipitation. The dibromide, (5-Anthracen-9-yl-3-dibromomethylene-penta-1,4-diynyl)-triisopropyl-silane (VIII), was isolated as a pale yellow oil (150 mg, 64 %). The dibromide was carried on directly to the next step.
Step 8: nBuLi (235 uL, 2.27 M, 0.53 mmol) was added to a 78 C solution of dibromide VIII (150 mg, 0.26 mmol) in hexanes (10 mL) and the reaction mixture was slowly warmed to -40 oC. The reaction was quenched by adding NH4Cl(aq) and partitioned between ether and water. The organic phase was dried (MgSO4) and concentrated to yield 1i as a bright yellow solid (42 mg, 41%); Mp: 124 126 C; 1H NMR (200 MHz, CDCl3) d 8 . 4 8 ( s , 1 H ) , 8 . 4 2 ( d , J = 3 . 8 H z , 2 H ) , 7 . 9 7 ( d , J = 8 . 0 H z , 2 H ) , 7 . 5 4 ( m , 4 H ) , 1 . 1 2 ( s , 2 1 H ) ; 1 3 C N M R ( 1 2 5 M H z , C D C l 3 ) d 1 3 4 . 7 ( s ) , 1 3 0 . 9 ( s ) , 1 2 9 . 4 , ( d ) , 1 2 8 . 9 ( d ) , 1 2 7 . 5 ( d ) , 1 2 6 . 3 ( d ) , 1 2 5 . 9 ( d ) , 1 1 4 . 4 ( s ) , 8 9 . 8 ( s ) , 8 8 . 5 ( s ) , 8 5 . 1 ( s ) , 7 4 . 0 ( s ) , 7 0 . 4 (s), 60.8 (s), 18.5 (q), 11.3 (d); MS (EI) m/z 406 (M+), 363, 321, 293, 253, 153, 112, 70; HRMS calc'd for C29H30Si 406.2118 (M+), found 406.2100.
1,8-Diphenyl-octa-1,3,5,7-tetrayne (2b)
Compound 1b (100 mg, 0.35 mmol), Cu(OAc)2 (192 mg, 1.05 mmol) and TBAF (1.0 M in THF, 355 mL ) w e r e c o m b i n e d i n a m i x t u r e o f p y r i d i n e / d i e t h y l e t h e r ( 3 : 1 , 1 0 0 m L ) a t 2 2 C a s p e r t h e s t a n d a r d m e t h o d . C h r o m a t o g r a p h y y i e l d e d t h e t i t l e c o m p o u n d a s a y e l l o w s o l i d ( 4 0 m g , 9 1 % ) ; 1 H N M R ( 5 0 0 M H z , C D C l 3 ) 7 . 5 4 7 . 5 1 ( m , 2 H ) , 7 . 4 2 7 . 3 7 ( m , 1 H ) , 7 . 3 6 7 . 3 2 ( m , 2 H ) ; 1 3 C N M R ( 1 2 5 M H z , C D C l 3 ) 1 3 3 . 2 ( d ) , 1 3 0 . 0 ( d ) , 1 2 8 . 5 ( d ) , 1 2 0 . 5 ( s ) , 7 7 . 7 ( s ) , 7 4 . 4 ( s ) , 6 7 . 1 ( s ) , 6 3 . 6 ( s ) ; M S ( E I ) m / z 2 5 0 ( M + ) , 2 2 6 , 1 6 2 , 1 2 5 ; H R M S c a l c ' d f o r C 2 0 H 1 0 2 5 0 . 0 7 8 3 ( M + ) , f o u n d 2 5 0 . 0 7 8 4 .
1 , 8 - D i - ( o - b r o m o p h e n y l ) - o c t a - 1 , 3 , 5 , 7 -tetrayne (2d)
Compound 2a (500 mg, 1.58 mmol), Cu(OAc)2 (856 mg, 4.73 mmol) and TBAF (1.0 M in THF, 1.58 mL) were combined in pyridine/diethyl ether (3:1, 500 mL) at 22 C as per the standard method. Chromatography yielded the title compound as a pale yellow solid (232 mg, 92 %); 1H NMR (500 MHz, CDCl3) d 7 . 5 8 ( d , J = 0 . 8 H z , 1 H ) , 7 . 5 4 ( m , 1 H ) , 7 . 2 8 - 7 . 1 9 ( m , 2 H ) ; 1 3 C N M R ( 1 2 5 M H z , C D C l 3 ) d 1 3 5 . 1 ( d ) , 1 3 2 . 7 ( d ) , 1 3 0 . 9 ( d ) , 1 2 7 . 2 ( d ) , 1 2 6 . 8 ( s ) , 1 2 3 . 1 ( s ) , 7 8 . 3 ( s ) , 7 6 . 0 ( s ) , 6 8 . 5 ( s ) , 6 4 . 0 ( s ) ; M S ( E I ) m / z 4 0 7 ( M + ) , 3 8 3 , 3 5 9 , 3 0 3 , 2 6 7 , 2 4 8 , 2 2 4 , 1 9 8 , 1 1 2 , 7 5 , 3 9 ; H R M S c a l c ' d f o r C 2 0 H 8 B r 2 4 0 5 . 8 9 9 2 ( M + ) , f o u n d 4 0 5 . 9 0 1 0 . X - r a y s t r u c t u r a l a n a l y s e s f o r c o m p o u n d 2 d : C r y s t a l s i z e 0 . 2 2 x 0 . 1 8 x 0 . 0 7 m m 3 , t r i c l i n i c , s p a c e g r o u p P - 1 , s c a n r a n g e 2 . 9 2 < 2 q < 2 8 . 6 9 , a = 3 . 9 2 4 3 ( 6 ) , b = 7 . 1 8 6 8 ( 1 2 ) , c = 1 4 . 3 5 4 ( 2 ) , = 1 0 3 . 0 0 8 ( 3 ) , V = 3 9 2 . 0 1 ( 1 1 ) 3 , Z = a , rc a l c d = 1 . 7 2 9 g c m - 3 , u = 5 . 1 6 2 m m - 1 , 1 7 7 1 u n i q u e r e f l e c t i o n s a t 8 0 C , o f w h i c h 3 0 5 9 w e r e t a k e n a s o b s e r v e d [ I o > 2 . 0 0 s( I ) ] , R = 0 . 0 5 3 0 , R w = 0 . 1 1 3 7 . C r y s t a l l o g r a p h i c d a t a ( e x c l u d i n g s t r u c t u r e f a c t o r s ) f o r t h e s tructures reported in this paper have been deposited with the Cambridge Crystallographic Data Center as supplementary publication no. CCDC-163717 (2d). Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: (+44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
1,8-Di-(m-dibutylaminophenyl) -octa-1,3,5,7-tetrayne (2e)
Compound 2b (100 mg, 0.24 mmol), Cu(OAc)2 (133 mg, 0.73 mmol) and TBAF (1.0 M in THF, 100 mL ) w e r e c o m b i n e d i n p y r i d i n e / d i e t h y l e t h e r ( 3 : 1 , 1 0 0 m L ) a t 2 2 C a s p e r t h e s t a n d a r d m e t h o d . C h r o m a t o g r a p h y y i e l d e d t h e t i t l e c o m p o u n d a s a y e l l o w o i l ( 5 0 m g , 8 2 % ) ; 1 H N M R ( 2 0 0 M H z , C D C l 3 ) 7 . 1 2 ( t , J = 8 . 0 H z , 2 H ) , 6 . 8 1 6 . 6 7 ( m , 6 H ) , 3 . 2 2 ( t , J = 7 . 5 H z , 8 H ) , 1 . 6 3 1 . 4 2 ( m , 8 H ) , 1 . 4 2 1 . 2 2 ( m , 8 H ) , 0 . 9 7 ( t , J = 7 . 1 H z , 1 2 H ) ; 1 3 C N M R ( 5 0 M H z , C D C l 3 ) 1 4 7 . 8 ( s ) , 1 2 9 . 3 ( d ) , 1 2 0 . 8 ( s ) , 1 2 0 . 0 ( d ) , 1 1 5 . 4 ( d ) , 1 1 3 . 6 ( d ) , 7 9 . 0 ( s ) , 7 3 . 1 ( s ) , 6 6 . 8 ( s ) , 6 3 . 7 ( s ) , 5 0 . 6 ( t ) , 2 9 . 2 ( t ) , 2 0 . 3 ( t ) , 1 4 . 0 ( q ) ; M S ( E I ) m / z 5 0 6 ( M + ) , 4 6 1 , 4 1 9 , 2 2 9 , 1 8 6 ; H R M S c a l c ' d f o r C 3 6 H 4 4 N 2 5 0 6 . 3 5 0 4 ( M + ) , f o u n d 5 0 6 . 3 5 8 6 .
1 , 8 - D i - ( 1 - n a p h t h y l ) - o c t a - 1 , 3 , 5 , 7 - t e t r a y n e ( 2 f )
C o m p o u n d 2 d ( 1 5 0 m g , 0 . 4 5 m m o l ) , C u ( O A c ) 2 ( 2 4 5 m g , 1 . 3 6 m m o l ) a n d T B A F ( 1 . 0 M i n T H F , 4 5 1 mL ) w e r e c o m b i n e d i n p y r i d i n e / d i e t h y l e t h e r ( 3 : 1 , 1 3 6 m L ) a t 2 2 C a s p e r t h e s t a n d a r d m e t h o d . C h r o m a t o g r a p h y y i e l d e d t h e t i t l e c o m p o u n d a s a b r i g h t y e l l o w s o l i d ( 7 6 m g , 9 6 % ) ; 1 H N M R ( 2 0 0 M H z , C D C l 3 ) d 8 . 3 2 ( d , J = 7 . 9 , 2 H ) , 7 . 8 6 ( m , 4 H ) , 7 . 3 7 - 7 . 6 8 ( m , 8 H ) ; 1 3 C N M R ( 5 0 M H z , C D C l 3 ) d 1 3 4 . 2 ( s ) 1 3 3 . 3 ( d ) , 1 3 3 . 0 ( s ) , 1 3 0 . 6 ( d ) , 1 2 8 . 6 ( d ) , 1 2 7 . 4 ( d ) , 1 2 6 . 8 ( d ) , 1 2 5 . 9 ( d ) , 1 2 5 . 1 ( d ) , 1 1 8 . 1 ( s ) , 7 9 . 0 3 ( s ) , 7 9 . 0 ( s ) , 7 7 . 7 ( s ) , 7 6 . 5 ( s ) ; M S ( E I ) m / z 3 5 0 ( M + ) , 3 2 6 , 3 0 2 , 2 7 9 , 1 4 9 , 8 5 , 7 1 , 2 9 ; H R M S c a l c ' d f o r C 2 8 H 1 4 3 5 0 . 1 0 9 6 ( M + ) , f o u n d 3 5 0 . 1 0 9 5 .
H e x a d e c a - 5 , 7 , 9 , 1 1 - t e t r a y n e ( 2 g )
C o m p o u n d 2 e ( 1 2 0 m g , 0 . 4 6 m m o l ) , C u ( O A c ) 2 ( 2 5 0 m g , 1 . 3 7 m m o l ) a n d T B A F ( 1 . 0 M i n T H F , 4 6 0 mL ) w e r e c o m b i n e d i n p y r i d i n e / d i e t h y l e t h e r ( 3 : 1 , 1 4 0 m L ) a t 2 2 C a s p e r t h e s t a n d a r d m e t h o d . C h r o m a t o g r a p h y y i e l d e d t h e t i t l e c o m p o u n d a s a c l e a r l i q u i d ( 4 8 m g , 9 8 % ) ; 1 H N M R ( 2 0 0 M H z , C D C l 3 ) d 2 . 2 5 ( t , J = 6 . 7 , 2 H ) , 1 . 4 8 ( m , 2 H ) , 1 . 0 5 ( s , 2 1 H ) , 1 . 0 5 ( m , 2 H ) , 0 . 8 8 ( t , J = 6 . 8 , 3 H ) ; 1 3 C N M R ( 5 0 M H z , C D C l 3 ) d 8 0 . 3 ( s ) , 6 5 . 6 ( s ) , 6 1 . 3 ( s ) , 6 0 . 5 ( s ) , 2 9 . 9 ( t ) , 2 1 . 8 ( t ) , 1 9 . 1 ( t ) , 1 3 . 4 ( t ) ; M S ( E I ) m / z 2 1 0 ( M + ) , 1 6 5 , 1 5 2 , 8 0 , 2 9 ; H R M S c a l c ' d f o r C 1 6 H 1 8 2 1 0 . 1 4 0 9 ( M + ) , f o u n d 2 1 0 . 1 4 2 9 .
1 , 8 - D i - ( 2 - t h i o p h e n y l ) - o c t a - 1 , 3 , 5 , 7 - t e t r a y n e ( 2 h )
C o m p o u n d 2 f ( 9 0 m g , 0 . 3 1 m m o l ) , C u ( O A c ) 2 ( 3 7 5 m g , 0 . 9 3 m m o l ) a n d T B A F ( 1 . 0 M i n T H F , 7 0 0 mL ) w e r e c o m b i n e d i n p y r i d i n e / d i e t h y l e t h e r ( 3 : 1 , 2 0 0 m L ) a t 2 2 C a s p e r t h e s t a n d a r d m e t h o d . C h r o m a t o g r a p h y y i e l d e d t h e t i t l e c o m p o u n d a s b r i g h t y e l l o w c r y s t a l s ( 3 3 m g , 8 2 % ) ; 1 H N M R ( 2 0 0 M H z , C D C l 3 ) d 7 . 3 9 ( d d , J = 5 . 7 , 4 . 5 H z , 1 H ) , 7 . 3 2 ( t , J = 4 . 5 H z , 1 H ) , 6 . 9 7 ( t , J = 4 . 5 H z , 1 H ) ; 1 3 C N M R ( 5 0 M H z , C D C l 3 ) d 1 3 6 . 2 ( d ) , 1 3 0 . 1 ( d ) , 1 2 7 . 3 ( d ) , 1 2 0 . 9 ( d ) , 7 8 . 8 ( s ) , 7 1 . 3 ( s ) , 6 4 . 6 ( s ) , 6 1 . 6 ( s ) ; M S ( E I ) m / z 2 3 8 , 2 1 4 , 1 6 9 , 1 5 0 , 1 2 2 , 6 9 , 2 9 ; H R M S c a l c ' d f o r C 1 4 H 6 S 2 2 3 7 . 9 9 1 1 ( M + - C 2 ) , f o u n d 2 3 7 . 9 8 9 7 .
D i b u t y l - [ 4 - i o d o - 3 - ( 4-triisopropylsilanyl-buta-1,3-diynyl)-phenyl]-amine (4)
Dibutyl-[3-(4-triisopropylsilanyl-buta-1,3-diynyl)-phenyl]-amine (4.50 g, 11.0 mmol), BnNMe3ICl2 (3.83 g, 11.0 mmol), and CaCO3 (1.54 g, 15.4 mmol) were added to a mixture of CH2Cl2/methanol (5:1, 90 mL) and stirred at 22 C for 3 h. Excess CaCO3 was removed by filtration and the filtrate was concentrated. The crude yellow oil was partitioned between ether and Na2S2O3 (10 % aq) and the organic phase was washed with water and brine, dried, and concent r a t e d . C h r o m a t o g r a p h y ( h e x a n e s / C H 2 C l 2 , 2 : 1 ) a f f o r d e d t h e t i t l e c o m p o u n d a s a y e l l o w o i l ( 4 . 4 1 g , 7 5 % ) ; 1 H N M R ( 5 0 0 M H z , C D C l 3 ) 7 . 4 8 ( d , J = 8 . 5 H z , 1 H ) , 6 . 7 7 ( s , 1 H ) , 6 . 3 5 ( s , 1 H ) , 3 . 1 8 ( t , J = 7 . 6 H z , 4 H ) , 1 . 5 3 1 . 4 7 ( m , 4 H ) , 1 . 3 5 1 . 2 8 ( m , 4 H ) , 1 . 1 1 ( s , 2 1 H ) , 0 . 9 3 ( t , J = 7 . 3 H z , 6 H ) ; 1 3 C N M R ( 1 2 5 M H z , C D C l 3 ) 1 4 7 . 6 ( s ) , 1 3 8 . 9 ( d ) , 1 2 8 . 2 ( s ) , 1 1 9 . 7 ( s ) , 1 1 7 . 3 ( d ) , 1 1 4 . 9 ( d ) , 8 9 . 6 ( s ) , 8 2 . 0 ( s ) , 7 7 . 7 ( s ) , 7 6 . 5 ( s ) , 5 0 . 7 ( t ) , 2 9 . 1 ( t ) , 2 0 . 3 ( t ) , 1 8 . 6 ( q ) , 1 3 . 9 ( q ) , 1 1 . 3 ( d ) ; M S ( E I ) m / z 5 3 5 ( M + ) , 3 8 8, 345, 319, 162; HRMS calcd for C27H42INSi 535.2131 (M+), found 535.2136.
Acetylenic Precursor 5
A solution of 4 (4.00 g, 7.47 mmol) in THF (200 mL) was degassed by bubbling argon through the solution for 30 min. CuI (200 mg, 1.05 mmol), Pd(PPh3)2Cl2 (600 mg, 0.85 mmol), and Et3N (40 mL) were added to the degassed solution and stirred at 22 C for 10 min. 1,4-diethynylbenzene (460 mg, 3.64 mmol) was added to the solution and the reaction was heated at reflux for 18 h. The reaction was cooled, filtered t h r o u g h a s i l i c a g e l p l u g , a n d c o n c e n t r a t e d . C h r o m a t o g r a p h y ( h e x a n e s / C H 2 C l 2 , 2 . 5 : 1 ) a f f o r d e d 5 a s a b r i g h t y e l l o w s o l i d ( 8 0 6 m g , 2 4 % ) ; 1 H N M R ( 5 0 0 M H z , C D C l 3 ) d 7 . 4 4 ( s , 4 H ) , 7 . 3 1 ( d , J = 8 . 8 H z , 2 H ) , 6 . 7 2 ( s , 2 H ) , 6 . 5 6 ( d , J = 7 . 6 H z , 2 H ) , 3 . 2 4 ( t , J = 7 . 7 H z , 8 H ) , 1 . 5 7 1 . 5 1 ( m , 8 H ) , 1 . 3 7 1 . 3 0 ( m , 8 H ) , 1 . 1 2 ( s , 4 2 H ) , 0 . 9 5 ( t , J = 7 . 3 H z , 1 2 H ) ; 1 3 C N M R ( 1 2 5 M H z , C D C l 3 ) d 1 4 7 . 4 ( s ) , 1 3 2 . 7 ( d ) , 1 3 1 . 1 ( d ) , 1 2 5 . 0 ( s ) , 1 2 3 . 0 ( s ) , 1 1 4 . 9 ( d ) , 1 1 3 . 2 ( s ) , 1 1 2 . 4 ( d ) , 9 1 . 7 ( s ) , 9 0 . 7 ( s ) , 8 9 . 8 ( s ) , 8 8 . 3 ( s ) , 7 7 . 1 (s), 75.3 (s), 50.6 (t), 29.3 (t), 20.2 (t), 18.5 (q), 13.9 (q), 11.3 (d); MS (ES) m/z 941.3 (M+), 734.1, 610.1, 285.9; Anal. calcd for C64H88N2Si2: C 81.04, H 9.42, found C 81.64, H 9.40.
Macrocycles 6 (Dimer) and 7 (Monomer)
Compound 5 (508 mg, 0.54 mmol), Cu(OAc)2 (590 mg, 3.23 mmol) and TBAF (1.0 M in THF, 1.19 mL) were combined in pyridine/diethyl ether (100 mL) at 22 C as per the standard method. Chromatography (petroleum ether/CH2Cl2, 2:1) yielded 6 as an orange solid (16 mg, 5 %) and 7 as a red s o l i d ( 1 5 5 m g , 4 6 % ) ; f o r 6 ; 1 H N M R ( 5 0 0 M H z , C D C l 3 ) d 7 . 7 0 ( s , 4 H ) , 7 . 1 9 ( d , J = 8 . 4 H z , 2 H ) , 6 . 5 4 ( d , J = 8 . 4 H z , 2 H ) , 6 . 5 0 ( s , 2 H ) , 3 . 2 1 ( t , J = 7 . 7 H z , 8 H ) , 1 . 5 4 1 . 4 8 ( m , 8 H ) , 1 . 3 5 1 . 2 8 ( m , 8 H ) , 0 . 9 3 ( t , J = 7 . 3 H z , 1 2 H ) ; 1 3 C N M R ( 1 2 5 M H z , C D C l 3 ) d 1 4 7 . 3 5 ( s ) , 1 3 1 . 7 3 ( d ) , 1 3 1 . 0 1 ( d ) , 1 2 6 . 0 6 ( s ) , 1 2 3 . 3 5 ( s ) , 1 1 6 . 4 7 2 ( s ) , 1 1 2 . 9 2 ( d ) , 1 1 2 . 3 1 ( d ) , 9 3 . 8 9 ( s ) , 9 2 . 4 9 ( s ) , 8 6 . 8 8 ( s ) , 7 8 . 4 6 ( s ) , 7 1 . 4 3 ( s ) , 7 1 . 0 7 ( s ) , 5 0 . 6 8 ( t ) , 2 9 . 1 8 ( t ) , 2 0 . 1 9 ( t ) , 1 3 . 8 7 ( q ) ; M S ( E S ) m / z 6 2 7 . 1 ( M + ) , 3 1 4 . 3 , 1 4 4 . 8 , 7 2 . 9 ; f o r 7 ; 1 H N M R ( 5 0 0 M H z , C D C l 3 ) 7 . 4 9 ( s , 8 H ) , 7 . 2 9 ( d , J = 8 . 9 H z , 4 H ) , 6 . 7 3 ( d , J = 2 . 1 H z , 4 H ) , 6 . 5 9 ( d , J = 6 . 8 H z , 4 H ) , 3 . 2 4 ( t , J = 7 . 6 H z , 1 6 H ) , 1 . 5 7 1 . 5 0 ( m , 1 6 H ) , 1 . 3 6 1 . 2 9 ( m , 1 6 H ) , 0 . 9 4 ( t , J = 7 . 3 H z , 2 4 H ) 1 3 C N M R ( 1 2 5 M H z , C D C l 3 ) 1 4 7 . 4 2 ( s ), 132.85 (d), 131.3 (d), 124.1 (s), 123.0 (s), 115.5 (s), 113.5 (d), 113.1 (d), 91.6 (s), 90.1 (s), 77.3 (s), 67.5 (s), 67.8 (s), 64.1 (s), 50.6 (t), 29.2 (t), 20.2 (t), 13.9 (q).
Spath, E. Sitzungsber. Akad. Wiss. Wien. Math.-Naturwiss. Kl., Abt. 2B 1911, 120, 117.
Lu, Y.F.; Harwig, C.W.; Fallis, A.G. J. Org. Chem. 1993, 58, 4202.
Eisler, S.; Tykwinski, R.R. J. Am. Chem. Soc. 2000, 122, 10736.
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