3422
J. Am. Chem. SOC. 1995, 117, 3422-3431
Acylpalladation of Intemal Alkynes and Palladium-Catalyzed Carbonylation of (2)-P-Iodoenones and Related Derivatives Producing y-Lactones and y-Lactamst Christophe CopCret, Takumichi Sugihara, Guangzhong Wu, Izumi Shimoyama, and Ei-ichi Negishi" Contribution from the Department of Chemistry, Purdue University, West Lafayette, Indiana 47907 Received December 19, 1994@
Abstract: The reaction of either an internal alkyne-organic halide mixture or (Z)-p-iodoenones with CO in the presence of a Pd-phosphine catalyst, e.g., Cl*Pd(PPh3)2, can give one of the three discrete types of compounds as the major products depending on the substrate structure and the reaction conditions. Those substrates which are convertible to (2)-y-oxo-a$-unsaturated acylpalladium derivatives lacking 6-H atoms are converted to the corresponding 2-butenolides (13)in the presence of water, which serves as a H donor. Carbon monoxide most likely is the source of two electrons. Either in the absence of water (or any other suitable H source) or in the presence of some factors disfavoring the butenolide formation, the same reaction gives the corresponding dimeric product (16). Even in cases where there is an a-H atom in the a-substitutent, 1,4-elimination products (ll),reported to be the major products in a related Pd-catalyzed reaction of terminal alkyne-aryl iodide mixtures with CO, were not detected. In sharp contrast, those substrates which can give rise to (a-y-oxo-a$-unsaturated acylpalladium derivatives containing 6-H atoms give, under comparable reaction conditions, enol lactones (12),Le., (Q-3-alkylidene2-butenolides, contaminated with only very minor amounts of 22 even in cases where an excess (4 equiv) of water was present. The required (a-p-iodoenones can be readily prepared in one pot via ZrCp2-promoted cyclization of alkynes with nitriles. The ready availability of the starting compounds and the high Z stereoselectivity make the overall sequence an attractive synthetic route to 12. The courses of the Pd-catalyzed carbonylation reactions of (Z)-p-iodo-a,p-unsaturatedimines 23 closely parallel the reactions of enones and produce the corresponding lactams, i.e.. 24 and 25.
Over the past decade, acylpalladationl of alkenes2 has been developed as a useful method for preparing cyclic compound^.^,^ In our own studies, three competitive acylpalladation reactions which are thought to proceed as shown in Scheme 1 have been discovered and d e ~ e l o p e d . ~ On the other hand, relatively little is known about acylpalladation of alkyne^.^ We have recently found that, under Pdcatalyzed carbonylation conditions in the presence of MeOH,3b 1 does not produce 2.6 The only monomeric cyclization product was 3,the formation of which does not involve acylpalladation. A Pd-catalyzed carbonylation reaction of a special class of +Presentedin a preliminary form at W A C Symposium OMCOS-7 in Kobe, Japan, September 1993. Abstract published in Advance ACS Abstracts, March 1, 1995. (1) Acylpalladation may be defined as addition of acylpalladium bonds to alkenes and alkynes. (2) For earlier papers on polymerization via acylpalladation, see: (a) Tsuji, J.; Hosaka, S. J. Polym. Lett. 1965, 3, 705. (b) Sen, A.; Lai, T. J. Am. Chem. SOC. 1982, 104, 3520. (3) (a) Negishi, E.; Miller, J. A. J. Am. Chem. SOC. 1983, 105,6761. (b) Tour, J. M.; Negishi, E. J. Am. Chem. SOC. 1985, 107, 8289. (c) Negishi, E.; Tour, J. M. Tetrahedron Lett. 1986,27,4869. (d) Negishi, E.; Sawada, H.; Tour, J. M.; Wei, Y. J. Org. Chem. 1988, 53, 913. (e) Zhang, Y.; O'Connor, B.; Negishi, E. J. Org. Chem. 1988, 53, 5588. (0 Negishi, E.; Wu, G.; Tour, J. M. Tetrahedron Lett. 1988, 29, 6745. (g) Wu, G.; Shimoyama, I.; Negishi, E. J. Org. Chem. 1991, 56, 6506. (4) For related papers by other workers, see: (a) Brewis, S.; Hughes, P. R. J. Chem. SOC., Chem. Commun. 1965,489. (b) Oppolzer, W.; Keller, T. H.; Bedoya-Zurita, M.; Stone, C. Tetrahedron Lett. 1989, 30, 5883. (c) Oppolzer, W. Pure Appl. Chem. 1990, 62, 1941. (d) Oppolzer, W.; Keller, T. H.; Kuo, D. L.; Pachinger, W. Tetrahedron Lett. 1990, 31, 1265. (e) Oppolzer, W.; Xu, J.; Stone, C. Helv. Chim. Acta 1991, 74, 465. (0 Ihle, N. C.; Heathcock, C. H. J. Org. Chem. 1993, 58, 560. (g) For related Nicatalyzed carbonylative cyclization, see: Camps, F.; Coll, J.; Llebaria, A,; Moret6, J. M. Tetrahedron Lett. 1988,29,5811. Camps, F.; Coll, J.; Moretb, J. M.; Toras, J. J. Org. Chem. 1989, 54, 1969. Llebania, A,; Camps, F.; Moret6, J. M. Tetrahedron Lett. 1993, 44, 1283.
terminal alkynes, i.e., benzylethynes, with aryl iodides was recently reported to give 4.' This reaction however is thought
1
2
*
to proceed not via acylpalladation but via 1-benzyl-2-benzoylethynes formed by Pd-catalyzed carbonylative coupling. Thus, the feasibility of acylpalladation of alkynes has remained undemonstrated.* In order to probe the feasibility of acylpalladation of alkynes, we chose to investigate the reaction of internal alkynes with organic halides, e.g., iodides, and CO in the presence of catalytic amounts of Pd-phosphine complexes, e.g., Pd(PPh3)4. One crucial question to be answered was whether or not acylpalladium species that can be generated in situ via oxidative addition of organic halides to Pd followed by CO insertion would (5) Related studies with Pd and Rh complexes. (a) Pd: Tsuji, J.; Nogi, T. J. Am. Chem. SOC. 1966.88, 1289. (b) Rh: Hong, P.; Mise, T.; Yamazaki, H. Chem. Lett. 1981, 989. (c) Rh: Doyama, K.; Joh, T.; Onitsuka, K.; Shiohara, T.; Takahashi, S. J. Chem. SOC., Chem. Commun. 1987, 649. (6) Zhang, Y.; Negishi, E. J. Am. Chem. SOC. 1989, 111, 3454. (7) Huang, Y.; Alper, H. J. Org. Chem. 1991, 56, 4534.
QQQ2-7863l95/1517-3422$Q9.QQlQ 0 1995 American Chemical Society
J. Am. Chem. SOC., Vol. 117, No. 12, 1995 3423
Acylpalladation of Alkynes
Scheme 1
A
I
Type II nucleophiles
1
I
trapping by internal enolates
m
Scheme 2 R' F
R
C
R2
H
COY
O
10
p-elimination
CO + RCECR
RX
11
m
8
R and R' = carbon group. R3 = R2 - CH2. R4 = R - CH2. X = halogen. Y = nucleophile
12
undergo acylpalladation to give 5. If 5 could indeed be gen4-octyne (1 equiv) and CO (1-40 atm) in the presence of 5 mol % of ClzPd(PPh3)2, MeOH (4 equiv), and NEt3 (1.5-2 erated, it could then undergo insertion of the second molecule equiv) in benzene or DMF at 100 "C merely gave methyl of CO to produce 6. Alternatively, 5 could also be converted to oligo- and polyacetylenes (7) via cascade c a r b ~ p a l l a d a t i o n . ~ ~ ~ benzoate in 80- 100%yields without incorporation of 4-octyne. In cases where 5 contains a P-hydrogen which can be synThe use of hydroxy-containing alkynes, i.e., 3-pentyn-1-01 and coplanar with Pd, their dehydropalladation could give acylallenes o-((trimethylsilyl)ethynyl)phenol, in place of a combination of 4-octyne and MeOH also led to the formation of the corre8. However, our recent result^^.^ indicate that such a process sponding esters in 85-100% yields." We conclude that is generally unfavorable. More likely under the carbonylation alcoholysis of acylpalladium species is generally faster than conditions is a polymerization process producing 9, in which intermolecular acylpalladation of alkynes12 to produce 5. acylpalladation and CO insertion take place alternately. In order Interestingly, the reaction of 4-octyne with PhI and CO (10to obtain monomeric products via 6 , it would have to be trapped by external or internal nucleophiles including e n 0 1 a t e s ~ ~ ~tog J ~ 40 atm) in the absence of any alcohol under otherwise produce 10-12 (Scheme 2). Trapping by other reagents, such comparable conditions as above, i.e., in the presence of 5 mol % of ClzPd(PPh3)~and NEt3 (2 equiv) in DMF at 100-140 "C as alkenes, is also conceivable. for 12-24 h, gave 13a in varying yields. This product contains Results and Discussion two more hydrogen atoms than the corresponding 11 or 12. The use of an internal alkyne, Le., 4-octyne, precludes the mechanism With the goal of obtaining monomeric compounds via 6 , we involving carbonylative cross coupling proposed for the reaction initially attempted trapping of such intermediates by alcohols of terminal alkynes.' On the other hand, those that proceed to produce 10. However, the reaction of iodobenzene with via 5 and 6 appear plausible, even though the presumed (8) In our concurrent study on cyclic carbopalladation of alkynes, we conversion of 6a (R = Ph, R1 = R2 = n-Pr) into 13a requiring have recently observed a few examples of cyclic acylpalladation of alkynes incorporation of an external hydrogen atom presents a puzzle [Sugihara, T.; Coptret, C.; Owczarezyk, Z.; Harring, L. S.; Negishi, E. J. to be solved. The intermediacy of 6 was strongly supported Am. Chem. SOC.1994, 116, 79231. (9) (a) Zhang, Y.; Wu, G.; Agnel, G.; Negishi, E. J. Am. Chem. SOC. by conversion of 14a13 into 13a in nearly quantitative yield 1990, 112, 8590. (b) Negishi, E. Pure Appl. Chem. 1992, 74, 323. under essentially the same conditions as those mentioned above. (10) (a) Roberto, D.; Catellani, M.; Chiusoli, G. P. Tetrahedron Lett. 1988,29, 2115. (b) Negishi, E.; Zhang, Y.; Shimoyama, I.; Wu, G. J. Am. (11) These experiments were performed by Y. V. Gulevich in our Chem. SOC. 1989,111,8018. (c) Shimoyama, I.; Zhang, Y.; Wu, G.; Negishi, laboratories. (12) For some rare examples of intramolecular acylpalladation of alkynes E. Tetrahedron Lett. 1990, 31, 2841. (d) Uozumi, Y.; Mori, E.; Mori, M.; Shibasaki, M. J. Organomet. Chem. 1990,399,93. (e) Negishi, E.; CopBret, followed by alcoholysis, see ref 8. C.; Sughara, T.; Shimoyama, I.; Zhang, Y.; Wu, G.; Tour, J. M. Tetrahedron (13) Takahashi, T.; Kageyama, M.; Denisov, V.; Hara, R.; Negishi, E. 1994, 50, 425. Tetrahedron Lett. 1993, 34, 681. ~
3424 J. Am. Chem. SOC.,Vol. 117, No. 12, 1995
Copkret et al.
Table 1. Pd-Catalyzed Carbonylation of (a-/?-IodoalkenylAryl Ketones in the Presence of a Base"
R'
R'
R2
R2
/?-iodoenone 14a 14a 14c 14d
R'
R2
monomer
dimer
Ar
R'
R2
base
13
yield?,' %
16
yield? %
Ph Ph Ph p-To1
n-Pr n-Pr Ph H
n-Pr n-Pr Ph P-TolCHz
NEt3 Kzc03 NEt3 NEt3
13a 13a 13c 13d
99 1' 55 49
16a 16a 16c 16d
98% D incorporation; 'H NMR (CDC13, method B, 13h was formed in 65% NMR yield along with 20% of the Me&) 6 7.0-7.6 (m, 5 H); 13CNMR (cDcl3, Me4Si) 6 24.76 (t, J = starting alkyne. Chromatography on silica gel (80/20 pentaneEt20) 22 Hz),70.42 (t, J = 10 Hz),81.90 (bs), 126.64, 127.78, 128.48, 136.02. afforded 206 mg (64%) of an 89/11 regioisomeric mixture of 13h and A solution of 3-phenyl-1,3,3-trideuterio-l-propyne (0.41 g, 3.26 mmol) 3-@-anisyl)-2-butyl-4-phenyl-2-buten-4-olide.The spectral data for 13h in THF (3.0 mL) was treated with 2.6 M n-BuLi (1.33 mL, 3.45 mmol, are as follows: 'H NMR (CDCl3, Me4Si) 6 0.81 (t, J = 7.1 Hz, 3 H), -78 "C) followed 30 min later by a solution of a-deuteriobenzalde1.10-1.60 (m, 4 H), 2.08 (ddd, J = 14.3, 9.4, 5.4 Hz, 1 H), 2.60 (ddd, hyde2' (274 mg, 2.55 mmol) in THF (1.0 mL). The reaction mixture J = 14.2, 9.8, 6.0 Hz, 1 H), 3.83 (s, 3 H), 5.83 (s, 1 H), 6.98 (d, J = was warmed to 25 "C, treated with aqueous W C l , extracted with EtzO, 8.7 Hz,2 H), 7.20-7.35 (m, 2 H), 7.35-7.50 (m, 3 H), 7.46 (d, J = washed with brine, dried over MgS04, filtered, and evaporated. 8.8 Hz, 2 H); I3C NMR (cDc13, MeSi) 6 13.62, 22.65, 26.87, 29.94, Chromatography on silica gel (97/3 pentandethyl acetate) afforded 0.43 55.21, 83.59, 114.02, 122.29, 126.05, 127.10, 129.02, 129.39, 130.27, g (74%) of 1,4-diphenyl-l,4,4-trideuterio-2-butyn-l-ol:"98% D 134.95, 159.73, 163.37, 173.27; IR (neat) 1750 cm-l; high-resolution incorporation; 'H NMR (CDC13, Me4Si) 6 3.3 (bs, 1 H), 7.0-7.6 (m, MS calcd for C2lH2203 322.1569, found 322.1563. 10 H); I3C NMR (CDCl3, Me4Si) 6 24.2 (pent, J = 20 Hz), 63.9 (t, J = 22.5 Hz), 82.1, 84.4, 126.35, 126.40 (2C), 127.62, 127.82, 128.18 (9) 2,4-Di-@-anisyl)-3-butyl-2-buten-4-oiide (13i). Using method (2C), 128.25 (2C), 136.0 (t, J = 5 Hz),140.8; IR (neat) 3340 cm-I. B, 13i was formed in 65% N M R yield along with 32% of the starting alkyne. Thick layer chromatography on silica gel (50150 pentane/CHzTo a mixture of 1,4-diphenyl-l,4,4-trideuterio-2-butyn-l-ol (408 mg, 1.78 mmol), deuteriotriethylsilane (271 mg, 2.31 mmol), and N W CIZ)afforded 197 (56%) of an 91/9 regioisomeric mixture of 13i and (85 mg, 2.31 mmol) in CH2Cl2 (2.0 mL) was added at 0 "C a solution 3,4-Di-(p-anisyl)-2-butyl-2-buten-4-olide. The spectral data for 13i are in CHzClz (1.0 mL) over of CSCOOH (0.69 mL, 1.01 g, 8.90 "01) as follows: 'H NMR (CDCls, MeSi) 6 0.83 (t, J = 7.2 Hz, 3 H), a 10 min period.22 The reaction mixture was stirred for 2 h at 25 "C, 1.15-1.60 (m, 4 H), 2.08 (ddd, J = 14.4, 9.2,5.2 Hz, 1 H), 2.61 (ddd, treated with aqueous NaHC03, extracted with EtzO, dried over MgS04, J = 14.4, 9.8, 6.2 Hz, 1 H), 3.82 (s, 3 H), 3.86 (s, 3 H), 5.79 (s, 1 H), filtered, evaporated, and purified by chromatographyon silica gel (99/1 6.93 (d, J = 8.7 Hz, 2 H), 6.99 (d, J = 8.7 Hz, 2 H), 7.20 (d, J = 8.7 pentanelethyl acetate) to give 321 mg (86%) of bis(a,a-dideuterioHz, 2 H), 7.46 (d, J = 8.7 Hz, 2 H); I3C NMR (CDCl3, Me&) 6 13.61, 22.65, 26.93,29.84, 55.29 (2C), 83.36, 113.99, 114.40, 122.40, 126.76, benzy1)ethyne: 'H NMR (CDCl3, Me&) 6 7.0-7.5 (m, 10 H); I3C NMR (CDCl3, Me.&) 6 24.6 (pent, J = 20 Hz), 80.17, 126.78, 128.20, 127.63, 128.60, 130.27, 159.70, 160.38, 163.34, 173.20; IR (neat) 1750 128.76, 137.60; IR (neat) 710 cm-l. (s), 1670 (s) cm-'; high-resolution MS calcd for C22H2404 352.1675, found 352.1671. Preparation of (Z)-/?-Iodoenonesand (Z)-/?-Iodoenimin(a) es.(Z)(14a). Representative 01)2-@-Anisyl)-3-butyl-4-(p-(metho~c~bonyl)phenyl)-~buten-3-Iodo-l-phenyl-2-(n-propyl)-2-hexen-l-one A solution of Cp2ZrClz (1.46 g, 5.0 m o l ) in THF (20 Pr0~edure.l~ 4-olide (13j). Using method B, 13j was formed in 35% NMR yield mL) was successively treated with 1.0 M EtMgBr in THF (10 mL, 10 along with 45% of the starting alkyne. Thick layer chromatography "01, -78 "C, 1 h), 4-octyne (0.73 mL, 0.50 g, 5.0 mmol, -78 to 0 on silica gel (80/20 pentane/CHZClz) afforded 80 mg (21%) of an 91/9 regioisomeric mixture of 13j and 3-(p-anisyl)-2-butyl-4-(p-(methoxy- "C, 1 h), benzaldehyde (0.61 mL, 0.64 g, 6.0 m o l , 60 "C, 3 h), 12 (2.54 g, 10 "01, 0 "C, 12 h) in THF (5.0 mL), and 1 M HCI. The carbonyl)phenyl)-2-buten-4-olide. The spectral data for 13j are as reaction mixture was extracted with EtZO, washed successively with 1 follows: 'H N M R (cDcl3,Me.&) 6 0.82 (t, J = 7.1 Hz, 3 H), 1.1M HCl, aqueous NaHCO3, Na2S203, and NaC1, dried over MgS04, 1.6 (m, 4 H), 2.05 (ddd, J = 14.4, 9.3, 5.3 Hz, 1 H), 2.61 (ddd, J = filtered, and evaporated. Chromatography on silica gel (97/3 pentanel 14.3, 9.8, 6.0 Hz, 1 H), 3.85 (s, 3 H), 3.94 (s, 1 H), 5.87 (s, 1 H), 6.99 ethyl acetate) afforded 0.70 g (41%) of (Z)-3-iodo-l-phenyl-2-(n(d, J = 8.8 Hz, 2 H), 7.38 (d, J = 8.3 Hz, 2 H), 7.45 (d, J = 8.8 Hz, propyl)-2-hexen-l-ol: stereoselectivity > 98%; IH NMR (CDC13,Me42 H), 8.09 (d, J = 8.3 Hz, 2 H); I3C NMR (CDCl3, Me4Si) 6 13.59, Si) 6 0.76 (t, J = 7.3 Hz, 3 H), 0.8-1.1 (m, 4 H), 1.1-1.5 (m, 1 H), 22.66, 26.82, 30.00, 52.34, 55.34, 82.84, 114.10 (2C), 126.32, 127.04 1.63 (sex, J = 7.4 Hz, 2 H), 1.9-2.05 (m, 1 H), 2.05-2.25 (m, 2 H), (2C), 129.88, 130.29 (4C), 131.18, 140.00, 159.89, 162.75, 166.42, 2.2-2.5 (m, 2 H), 5.9-6.0 (m, 1 H), 7.2-7.4 (m, 3 H), 7.4-7.5 (m, 173.00; IR (neat) 1750 cm-l; high-resolution MS calcd for C23H2405 2 H); I3C NMR (CDCl,, Me&) 6 13.06, 14.43, 23.10, 23.87, 30.80, 380.1624, found 380.1632. 43.07, 82.48, 108.60, 125.25, 127.15, 128.09, 141.55, 145.12; IR (neat) (i) 4-Phenyl-3-(n-propyl)-2-(trimethylsilyl)-2-bu~n-4-o~de (13k). 3340 cm-'. Oxidation of this alcohol with pyridinium chlorochromate Using method A, 13k was formed in 39% NMR yield, regioisomeric (25 "C, 2 h) afforded 0.68 g (99%) of 14a: IH NMR (CDC13, ratio '94% along with 30% of the starting alkyne. Chromatography Me4Si) 6 0.90 (t, J = 7.5 Hz, 3 H), 1.03 (t, J = 7.5 Hz, 3 H), 1.45 on silica gel (97/3 pentaneEt20) afforded 85 mg (31%) of a >99/1 (sex, J = 7.5 Hz, 2 H), 1.68 (sex, J = 7.5 Hz, 2 H),2.3-2.5 (m. 2 H), regioisomeric mixture of 13k and 4-phenyl-2-(n-propyl)-3-(trimethyl2.6-2.7 (m, 2 H), 7.4-7.55 (m, 2 H), 7.55-7.7 (m, 1 H), 7.9-8.0 (m, silyl)-2-buten-4-olide. The spectral data for 13k are as follows: IH 2 H); 13C NMR (CDCl3, Me&) 6 13.07, 13.88, 21.73, 22.63, 34.46, NMR (CDC13, Me&) 6 -0.01 (s, 9 H), 1.01 (t. J = 7.4 Hz, 3 H), 41.66, 102.95, 128.73, 129.78, 133.40, 133.86, 146.24, 198.37; IR (neat) 1.55-1.75 (m, 2 H), 2.35-2.50 (m, 2 H), 5.78 (s, 1 H), 7.10-7.20 1668 cm-'. (m, 2 H), 7.30-7.40 (m, 3 H); I3C NMR (CDC13, MeSi) 6 -1.10, (b) (Z)-3-Iodo-1,2,3-triphenyl-2-propen-l-one (14c). (Z)-3-Iodo14.17, 22.54, 28.24, 86.78, 127.89, 128.71, 129.33, 135.31, 141.44, 1,2,3-triphenyl-2-propen1-01 was prepared using the procedure de162.02, 174.37; IR (neat) 1752 (s) cm-'; high-resolution MS calcd for scribed for 14a. Chromatography on silica gel (97/3 pentane/ethyl C16HzzOzSi274.1389, found 274.1386. acetate) afforded 615 mg (30%) of (Z)-3-iodo-1,2,3-triphenyl-2d) 4-cp-Anisyl)-~(n-propyl)-2-(~e~y~yl)-~bu~n~lide (131). propen-1-01: stereoselectivity >98%; IH NMR (CDC13, Me4Si) 6 2.33 Using method B, 131 was formed in 37% NMR yield, regioisomeric (d, J = 7 Hz, 1 H), 6.37 (d, J = 7 Hz, 1 H), 6.7-6.9 (m, 2 H), 6.9ratio >94%. Chromatography on silica gel (90110 pentaneEt20) 7.3 (m, 7 H), 7.3-7.5 (m, 4 H), 7.5-7.7 (m, 2 H); 13CNMR (CDC13, afforded 103 mg (34%) of a >99/1 regioisomeric mixture of 131 and Me4Si) 6 81.55, 102.65 (2C). 125.63(2C), 127.09, 127.29, 127.42 (2C), 4-(p-anisyl)-2-(n-propyl)-3-(trimethyls~yl)-2-buten-4-o~de. The spectral data for 131 are as follows: 'H NMR (CDC13, Me&) 6 0.03 (s, 9 (21) Kalvin, D. M.; Woodward, R. W. Tetrahedron 1984,40,3387. H), 1.02 (t, J = 7.4 Hz,3 H), 1.55-1.75 (m, 2 H), 2.35-2.55 (m, 2 (22) Olah,G. A.; Wang, Q.; Rakash, S. G.K. Synlett 1992,647. H),3.80 (s, 3 H), 5.77 (s, 1 H),6.80-6.90 (m, 2 H), 7.05-7.10 (m, 2 (23) Corey, E. J.; Suggs, J. W. Tetrahedron Lett. 1975,16, 2647.
Acylpalladation of Alkynes
J. Am. Chem. SOC., Vol. 117, No. 12, 1995 3429
127.45, 127.55 (2C), 128.21 (2C), 129.21 (2C). 130.26 (2C), 135.29, 0.53 g, 5.5 mmol, 0-25 "C, 1.5 h) were used in place of 4-octyne and 141.05, 143.81, 149.21; IR (neat) 3300 cm-l. Oxidation with PCCZ3 benzaldehyde, respectively. After iodinolysis, the reaction mixture was of (Z)-3-iodo-1,2,3-triphenyl-2-propen-l-ol (615 mg, 1.5 "01) gave treated with a 3 M HCl(25 "C, 3 h). After workup, chromatography 512 mg (84%) of 14c: IH NMR (CDC13, MeSi) 6 7.0-7.6 (m, 13 H), on silica gel (9515 pentaneEt20) afforded 0.84 g (60%) of 21f IH 7.5-7.7 (m, 2 H); I3C NMR (CDCl3, Me4Si) 6 98.59, 127.92, 128.12, NMR (CDCl3, Me4Si) 6 0.91 (t, J = 6.7 Hz, 3 H), 1.25-1.45 (m, 4 128.31, 128.38 (2C), 128.81 (2C), 128.90 (2C), 129.69 (2C), 130.14 H), 1.55-1.7 (m, 2 H), 1.85 (s, 3 H), 2.51 (s, 3 H), 2.65 (t. J = 7.4 (2C), 133.61, 133.70, 135.46, 141.78, 148.22, 196.17. Hz,2 H); 13CNMR (CDC13) 6 13.91, 16.50,22.45,23.05,23.10,31.29, (c) (Z)-4-Iodo-5-(n-propyl)-4-dodecen-6-one (21b). (2)-4-Iodo40.16, 115.13, 143.55, 208.68; IR (neat) 1702 cm-l. 5-(n-propyl)-4-dodecen-6-01was prepared using the procedure described (Z)-1,4-Bis@-tolyl)-3-iodo-2-buten-l-one (14d). A mixture of 2,3above for 14a. Chromatography on silica gel (97/3 pentane/ethyl butadien-1-01~~ (140 mg, 2.0 mmol), CUI(38 mg, 0.2 mmol), and Et20 acetate) afforded 334 mg (19%) of (Z)-4-iodo-5-(n-propyl)-4-do-decen(2.0 mL) was successively treated with 1.0 M p - T ~ l M g B rin~ ~THF 6-01: stereoselectivity >98%; 'H NMR (CDC13, Me4Si) 6 0.8-1.0 (m, 0 "C, 15 h), 12 (0.77 g, 3.0 mol, 2 h) in THF (10 (5.0 mL, 5.0 "01, 9 H), 1.2-1.65 (m, 14 H), 1.8-1.95 (br, 1 H), 2.0-2.15 (m, 1 H), mL), 1 M HC1, aqueous NaHC03, and Na2S203, dried over MgS04, 2.15-2.3 (m, 1 H), 2.4-2.6 (m, 2 H), 4.5-4.65 (m, 1 H); I3C NMR and evaporated. Chromatographyon silica gel (9/1 pentaneEt20) gave (CDCl3) 6 12.89, 14.06, 14.50,22.58,23.04,24.08,25.79,29.21,30.49, 251 mg (43%) of (Z)-3-iodo-4-(p-tolyl)-2-buten-l-ol: 'H NMR (CDC13, 31.76, 35.11, 42.93, 81.60, 106.36, 145.22; IR (neat) 3382 cm-l. Me&) 6 2.30 (s, 3 H), 2.67 (bs, 1 H), 3.78 (s, 2 H), 4.16 (d, J = 5.7 Oxidation with PCC23of (Z)-4-iodo-5-(n-propy1)-4-dodecen-6-o1(334 Hz, 2 H), 5.86 (t, J = 5.7 Hz, 1 H), 7.0-7.15 (m, 4 H); I3C NMR mg, 0.95 mmol) gave 249 mg (75%) of 21b: 'H NMR (CDC13, Me4Si) (CDC13, Me4Si) 6 21.04,50.93,67.04, 108.13, 128.84, 129.09, 134.74, 6 0.8-1.0 (m, 9 H), 1.2-1.5 (m, 8 H), 1.5-1.7 (m, 4 H), 2.2-2.3 (m, 134.78, 136.36; IR (neat) 3320 (bs), 1644 (s) cm-I. Oxidation of 2 H), 2.45-2.55 (m. 2 H), 2.6-2.7 (m, 2 H); 13C NMR (CDC13) 6 3-iodo-4-@-tolyl)-2-buten-l-ol(109 mg, 0.38 "01) with PCCz3 (0 12.82, 13.72, 13.98, 21.68, 22.46, 23.20, 28.72, 31.56, 33.39, 41.05, "C, 3 h) and chromatographyon silica gel (90/10 pentaneEt20) yielded 41.54, 100.43, 148.84, 208.31; IR (neat) 1700 cm-I. 85 mg (78%) of (Z)-3-iodo-4-(p-tolyl)-2-buten-l-al: 'H NMR (CDC13, (d)(Z)-l-Imino-3-iodo-l-phenyl-2-(n-propyl)-2-hexene (23a). This Me&) 6 2.33 (s, 3 H), 4.04 (s, 2 H), 6.18 (t, J = 6.4 Hz, 1 H), 7.07 compound was prepared according to the procedure described for 14a (d,J=7.95Hz,2H),7.15(d,J=7.95Hz,2H),9.55(d,J=6.4Hz, except that benzonitrile (0.63 mL, 0.63 g, 5.5 "01, 0-25 "C, 1.5 h) 1 H); I3C NMR (CDC13, Me&) 6 21.11, 53.19, 129.13, 129.53 (2C), was used in place of benzaldehyde. Chromatographyon silica gel (2/1 132.69, 133.13, 137.34, 197.71. (2)-3-Iod0-4-@-tolyl)-2-buten-1-ai (85 pentaneEt20) afforded 1.14 g (67%) of 23a: 'H NMR (CDC13,Me4mg, 0.30 mmol) in THF (1.0 mL) was treated with 1.0 M TolMgBr in Si) 6 0.88 (t, J = 7.3 Hz, 3 H), 1.02 (t, J = 7.3 Hz, 3 H), 1.40 (sex, THF (0.76 mL, 0.76 mmol, 0 "C, 1 h), diluted with EtzO, washed with J=7.4Hz,2H),1.69(sex,J=7.4Hz,2H),2.2-2.4(m,2H),2.65 1 M HC1 and aqueous NaHC03, dried over MgS04, and evaporated. (t, J = 7.4 Hz, 2 H), 7.35-7.5 (m, 3 H), 7.75-7.9 (m, 2 H), 9.1 (bs, Chromatography on silica gel (90/10 pentaneEt20) yielded 94 mg 1 H); 13CNMR (CDCl3) 6 13.15, 13.86, 21.93, 22.82, 34.19, 42.09, (82%) of (2)-1,4-bis(p-tolyl)-3-iodo-2-buten-l-ol. A mixture of (2)105.05, 127.80 (2C), 128.60 (3C), 130.94, 135.00, 180.36; IR (neat) 1,4-bis@-tolyl)-3-iodo-2-buten-l-ol(94 mg, 0.25 mmol) and DDQZ6 3238, 1632 cm-'. (114 mg, 0.50 "01) in dioxane (2.0 mL) was stirred for 48 h at 25 "C and evaporated. Chromatographyon silica gel (90/10 pentaneKH2(e) (Z)-2-Imino-4-iodo-3-(n-propyl)-3-heptene (23b). This compound was prepared according to the procedure described for 14a except Cl2) yielded 59 mg (63%) of 14d: 'H NMR (CDC13,Me&) 6 2.34 (s, that acetonitrile (0.29 mL, 205 mg, 5.5 mmol, 0-25 "C, 1.5 h) was 3 H ) , 2 . 3 9 ( ~ , 3 H ) , 4 . 0 5 ( d , J = l . l H z , 2 H ) , 7 . 1 0 ( t , J =l . l H z , l used in place of benzaldehyde. Chromatography on silica gel (50/50 H),7.16(~,4H),7.24(d,J=8.2Hz,2H),7.79(d,J=8.2Hz,2H); 13C NMR (CDC13, Me&) 6 21.16, 21.72, 53.44, 115.22, 128.79, pentaneEt20) afforded 0.85 g (61%) of 23b: 'H NMR (CDCl3, MerSi) 6 0.8-1.0 (m, 6 H), 1.35-1.5 (m, 2 H), 1.5-1.7 (m, 2 H), 2.15 (d, 129.17, 129.35, 129.47, 131.15, 134.21, 134.31, 136.97, 144.29, 190.49; IR (neat) 1664 (s) cm-l. J = 3.0 Hz, 3 H), 2.2-2.35 (m, 2 H), 2.45-2.6 (m, 2 H), 8.05 (bs, 1 H); I3CNMR (CDC13) 6 12.64, 13.55,21.46,22.37,24.78,33.03,41.52, o-Iodophenylp-Tolyl Ketone (17). A solution of o-iodobenzal101.19, 148.33, 182.55; IR (neat) 3238, 1632 cm-I. dehyde" (3.90 g, 16.8 mmol) in THF (15 mL) was successively treated (f) (Z)-3-(n-Propyl)-4-iodo-3-hepten-2-one (21a). A solution of with 1 M p-TolMgBr in THF (20 mL, 20 mmol.0 "C, 30 min) and 1 23b (160 mg, 0.50 "01) in a 5/1 mixture of THF13 N HC1 (4 mL) M HC1, extracted with Et20, washed with brine, dried over MgS04, was stirred 3 h at 25 "C, diluted with Et20, washed with aqueous filtered, and evaporated to give (o-iodopheny1)-p-tolylmethanolwhich NaHC03, dried over MgS04, and evaporated. Chromatography on was directly oxidized with PCCZ3(3 h, 25 "C). Chromatography on silica gel (98/2 pentaneEt20) afforded 122 mg (76%) of 21a: IH NMR silica gel (90/10 pentaneEt20) afforded 2.0 g (62%) of 17: IH NMR (CDC13, Me4Si) 6 0.93 (t, J = 7.1 Hz, 3 H), 0.95 (t, J = 7.2 Hz, 3 H), (CDC13, Me4Si) 6 2.42 (s, 3 H), 7.1-7.2 (m, 1 H), 7.2-7.35 (m, 3 H), 1.35-1.5 (m, 2 H), 1.5-1.7 (m, 2 H), 2.25-2.35 (m, 2H), 2.37 (s, 7.43 (dt, J = 7.5, 1.0 Hz, 1 H), 7.70 (dd, J = 6.5, 1.7 Hz, 2 H), 7.91 3H), 2.45-2.55 (m, 2H); I3C NMR (CDCl3) 6 12.84, 13.70, 21.62, (dd, J = 8.0,1.8 Hz, 1 H); I3C NMR (CDC13, Me4Si) 6 21.81, 92.18, 22.47, 28.9, 33.28,41.58, 100.19, 148.89,206.15; IR (neat) 1702 cm-I. 127.74, 128.28, 129.38, 130.60, 130.92, 133.05, 139.56, 144.62, 144.77, 196.86; IR (neat) 1668 (s), 1602 (s) cm-I. (8) (Z)-4-Imino-2-iodo-3-methyl-2-dodecene (23c). This compound was prepared according to the procedure described for 14a except that (Z)-l-Iodo-l-phenyl-2-(n-propyl)-l-penten-3-one (21c). Oxida2-butyne (0.39 mL, 270 mg, 5.0 mmol) and octyl cyanide (0.97 mL, tionZ3of (Z)-2-(n-propyl)-3-iodo-3-phenyl-2-propen1-01 (1.26 g, 4.17 0.77 g, 5.5 m o l , 0-25 "C, 1.5 h) were used in place of 4-octyne and "01) with PCCZ3afforded 0.93 g (74%) of (Z)-2-(n-propyl)-3-iodobenzaldehyde, respectively. Chromatography on silica gel (3/7 pentane/ 3-phenyl-2-propen-1-al: 'H NMR (CDC13, Me4Si) 6 0.73 (t, J = 7.3 EtzO) afforded 882 mg (55%) of 23c: 'H NMR (CDC13, Me&) 6 Hz, 3 H), 1.2-1.4 (m, 2 H), 2.1-2.25 (m, 2 H), 7.2-7.45 (m, 5 H), 0.88(t,J=7.1Hz,3H),1.1-1.5(m,12H),1.88(s,3H),2.35-2.45 9.76 (s, 1 H); I3CNMR (CDCl3) 6 13.79, 22.06, 30.69, 118.97, 126.77, (m, 2 H), 2.50 (s, 3 H), 8.03 (br, 1 H); I3C NMR (CDCl3) 6 13.87, 128.29, 128.82, 142.96, 143.44, 198.62; IR (neat) 1680 cm-I. (2)-217.13, 22.40, 24.77, 28.94, 29.04, 29.16, 29.35, 31.59, 36.63, 91.05, (n-Propyl)-3-iodo-3-phenyl-2-propen-l-al(405 mg, 1.35 "01) in THF 142.99, 186.07; IR (neat) 1622 cm-I. (4 mL) was treated with 1 M EtMgCl (2.0 mL, 2.0 m o l , 0 "C, 1 h) (h) (Z)-Z-Iodo-3-methyl-Z-dodecen-4-one (Zle). Hydrolysis of 23c in THF and 1 M HC1, diluted with EtzO, washed with NaHCO,, dried (178 mg, 0.50 mmol), using the procedure described for the preparation over MgS04, and evaporated. The crude oil was oxidized with PCCZ3 of 2la,afforded 21e in 160 mg (90%) after chromatography on silica (0 "C, 8 h) to give 164 mg (37%) of 21c: 'H NMR (CDCl3, Me4Si) 6 gel (95/5 pentanelEt20): 'H NMR (CDCl3, Me&) 6 0.88 (t. J = 6.6 0.78 (t, J = 7.3 Hz, 3 H), 1.22 (t, J = 7.3 Hz, 3 H), 1.3-1.45 (m. 2 Hz, 3 H), 1.2-1.4 (m, 10 H), 1.5-1.7 (m, 2 H), 1.84 (s, 3 H), 2.51 (s, H), 2.1-2.25 (m,2 H), 2.80 (q, J = 7.3 Hz, 2 H), 7.2-7.4 (m, 5 H); 3 H), 2.65 (t, J = 7.4 Hz, 2 H); I3C NMR (CDC13) 6 14.06, 16.43, (24) Olsson, L. I.; Claesson, A. Acta Chim. Scand. B 1977,31, 614. 22.56, 23.32,23.36,28.64, 28.89, 29.55, 31.61.40.13, 115.53, 143.49, (25) Duboudin, J. G.; Jausseaume, B.; Bonakdar, A. J . J. Organomet. 208.59; IR (neat) 1706 cm-'. Chem. 1979,168, 227. (i) (Z)-2-Iodo-3-methyl-Z-nonen-4-one (210. This compound was (26) Becker, H. D.; Bjork, A.; Adler, E. J. Org. Chem. 1980,45,1596. prepared according to the procedure described for 14a except that (27) Acheson, R. M.; Lee, G . C. M. J. Chem. Soc., Perkin Trans. I1987, 2-butyne (0.39 mL, 270 mg, 5.0 mmol) and hexanenitrile (0.66 mL, 2321.
(a-
3430 J. Am. Chem. Soc., Vol. 117, No. 12, 1995 13CNMR (CDCls) 6 7.55, 13.53, 21.41, 34.35, 34.58, 92.06, 128.07, 128.11, 128.23, 141.97, 151.05, 208.52; IR (neat) 1702 cm-I. (Z)-1,4-Diphenyl-3-(n-propyl)-4-iodo-3-buten-2-one (21d). (2)2-(n-Propyl)-3-iodo-3-phenyl-2-propen-l-al (see Zlc for preparation) (405 mg, 1.35 "01) in THF (4 mL) was treated with 2.0 M PhCH20 "C, 1 h) and 1 M HC1, diluted MgCl in THF (0.81 mL, 1.62 "01, with Et20, washed with NdCO3, dried over MgS04, and evaporated. Chromatography on silica gel (95/5 pentaneEtz0) afforded 148 mg 1-01as a byproduct (36%) of (Z)-2-(n-propyl)-3-iodo-3-phenyl-2-propenand 125 mg (24%) of (Z)-1,4-diphenyl-3-(n-propyl)-4-iodo-3-buten-201: 'H NMR (cDc13, Me4Si) 6 0.71 (t, J = 7.3 Hz, 3 H), 1.3-1.5 (m, 2 H), 1.83 (d, J = 2.2 Hz, 1 H), 2.0-2.3 (m, 2 H), 2.80 (dd, J = 10.0, 13.6 Hz, 1 H), 3.11 (dd, J = 3.3, 13.6 Hz, 1 H), 4.85-4.95 (m, 1 If), 7.15-7.45 (m, 10 H); 13CNMR (CDCl3) 6 14.28, 23.44, 31.56,41.92, 81.84, 96.76, 126.70, 127.57, 128.12, 128.20, 128.57, 129.51, 138.05, 144.52, 148.07; IR (neat) 3360 cm-l. Oxidation of (Z)-1,4-diphenyl3-(n-propy1)-4-iodo-3-buten-2-o1(125 mg, 0.32 "01) with PCC23(25 "C, 10 h) afforded after chromatography on silica gel (95/5 pentane/ EtzO) 78.8 mg (63%) of 21d: 'H NMR (CDCl3, Me4Si) 6 0.73 (t, J = 7.3 Hz, 3 H), 1.2-1.4 (m, 2 H), 2.0-2.1 (m, 2 H), 4.12 (s, 2 H), 7.27.4 (m, 10 H); I3C NMR (CDC13) 6 13.56, 21.39, 34.89,47.93,93.10, 127.19, 128.09, 128.26, 128.33, 128.49, 129.95, 133.06, 142.02, 150.56, 204.83; IR (neat) 1702 cm-I. (Z)-6-Iodo-5-decen-4-one (21g). (Z)-3-Iodo-2-hepten-l-al(l. 11 g, 4.69 "01) in THF (5.0 mL) was treated with 2.0 M n-PrMgC1 in Et20 (2.80 mL, 5.60 mm01,O "C, 1 h) and then 1 M HCl, diluted with Et20, washed with NaHC03, dried over MgS04, and evaporated. Chromatography on silica gel afforded 1.06 g (86%) of (Z)-6-iodo-5decen-4-01, which was oxidized with PCC23(25 "C, 6 h) to give 0.72 g (86%) of 21g: 'H NMR (CDC13, Me&) 6 0.93 (t, J = 7.3 Hz,3 H), 0.94 (t, J = 7.3 Hz, 3 H), 1.33 (sex, J = 7.4 Hz, 2 H), 1.5-1.8 (m, 4 H), 2.47 (t, J = 7.3 Hz, 2 H), 2.68 (t, J = 7.3 Hz,2 H), 6.68 (s, 1 H); I3C NMR (CDCl3) 6 13.56, 13.67, 17.06, 21.26, 31.25, 46.05, 47.51, 116.98, 130.32, 198.25; IR (neat) 1698 (s), 1464 (s) cm-'. (Z)-5-Iod0-6-@-tolyl)-ehexen-3-one(21h). (Z)-2-(n-Propyl)-3iodo-3-phenyl-2-propen-l-al(656 mg, 2.29 "01) in THF (10 mL) was treated with 2 M EtMgCl in THF (1.37 mL, 2.74 m o l , 0 "C, 1 h), quenched with 1 M HC1, diluted with Et-20,washed with NaHC03, dried over MgS04, and evaporated. Chromatographyon silica gel (9/1 pentaneEt20) afforded 694 mg (86%) of (Z)-5-iodo-6-(p-tolyl)-4-hexen3-01. which was directly oxidized with PCCZ3to give 617 mg (86%) of 21h: stereoselectivity >98%; 'H NMR (CDC13, Me4Si) 6 1.08 (t, J = 7.3 Hz, 3 H), 2.32 (s, 3 H), 2.49 (q, J = 7.2 Hz, 2 H), 3.97 (s, 2 H), 6.63 (s, 1 H), 7.0-7.15 (m, 4 H); 13C NMR (CDCl3) 6 7.80, 21.34, 37.67, 53.87, 114.91, 129.29, 129.57, 131.66, 134.33, 137.07, 199.21; IR (neat) 1702 (s) cm-'. Pd-Catalyzed Carbonylation of (Z)-/J-IodoalkenyIAryl Ketones. (a) 2,3-Di-(n-propyl)-4-phenyl-2-buten-4-olide (13a). Representative Procedure. (i) With Triethylamine as a Base (Method C). A mixture of 14a (86 mg, 0.25 mmol), Et3N (0.14 mL, 0.10 g, 1.0 mmol), 5 HzO (18 pL, 18 mg, 1.0 mmol), C12Pd(PPh& (8 mg, 0.012 "01, mol %), and benzene (1.O mL) was stirred at 120 "C under CO pressure (20 atm) for 12 h. The reaction mixture was treated with HzO, extracted with Et-20, dried over MgS04, filtered, and evaporated. Analysis by 'H NMR spectroscopy of the crude reaction mixture showed the formation of 13a in 95-99% yield. Chromatography on silica gel (97/3 pentane/ethyl acetate) yielded 51 mg (84%) of 13a: 'HNMR (CDC13, Me4Si)60.89(t,J=7.5Hz,3H),0.96(t,J=7.5Hz,3H), 1.2-1.6 (m, 2 H), 1.61 (sex, J = 7.5 Hz, 2 H), 1.96 (ddd, J = 14.4, 9.0, 5.4 Hz, 1 H),2.2-2.4 (m, 3 H), 5.68 (s, 1 H), 7.4-7.55 (m, 2 H), 7.557.7 (m, 1 H), 7.9-8.0 (m, 2 H); 13C NMR (CDCl3, Me&) 6 13.93, 14.05,21.27,21.58,25.62,28.53,83.73, 126.90, 127.23, 128.90, 129.19, 135.11, 163.20, 174.55; IR (neat) 1756, 1670 cm-'; high-resolution MS calcd for C1&2002 244.1463, found 244.1470. (ii) With Pyridine. Method C was modified by replacing NEt3 with pyridine (81 pL,79 mg, 1.0 m o l ) and omitting the addition of HzO and used to convert 14a to 13a in 58% NMR yield, with 21% of 14a remaining. (iii) With N,N-Diethyl-a,a-dideuteriobenzylamine.Using N,Ndiethyl-a,a-dideuteriobenzylamine (165 mg, 1.O "01) in place of NEt3
Copkret et al. and omitting the addition of H2O in method C, 14a was converted to 13a in 72% NMR yield. Incorporation of D at the y position was 98%; 'HNMR (CDC13, MeSi) 6 0.95 (t, J = 7.2 Hz, 3 H), 0.99 (t, J = 7.4 Hz, 3 H), 1.5-1.7 (m, 4 H), 2.25-2.35 (m, 2 H), 2.4-2.5 (m, 2 H), 4.82 (d, J = 2.7 Hz, 1 H), 5.07 (d, J = 2.7 Hz, 1 H);"C NMR (CDCl3) 6 13.96, 14.06, 21.45, 22.86, 25.82, 26.63, 92.51, 130.16, 150.64, 155.16, 170.26; IR (neat) 1772 cm-'; high-resolution MS calcd for CllH1602 180.1151, found 180.1156. @) (Z)-ZJ-Di-(n-propyl)-4-hexylidene-2-buten-4-olide (12b). Using method D, 12b was formed in 75% NMR yield. Chromatography on silica gel (99/1 pentaneEtz0) afforded 80 mg (70%) of 12b: stereoisomeric punty '98%; 'H NMR (CDCl3, Me&) 6 0.8-1.1 (m, 9 H),1.2-1.7 (m, 10 H), 2.2-2.5 (m, 6 H), 5.22 (t, J = 7.8 Hz, 1 H); I3C NMR (CDC13) 6 13.92, 14.05, 21.55, 22.34, 23.07, 25.70, 25.95, 26.50 (2C), 28.83, 31.41, 111.29, 127.79, 149.14, 150.94, 170.64; IR (neat) 1762 cm-'; high-resolution MS calcd for c 1 & 2 6 0 2 250.1934, found 250.1914.
Acylpalladation of Alkynes (c) (Z)-2-Phenyl-J-(n-propyl)-4-ethylidene-2-buten-4-olide (12c). Using method D, 12c was formed in 72% NMR yield. Chromatography on silica gel (97/3 pentaneEtz0) afforded 80 mg (70%) of 12c: stereoisomeric purity '98%; 'H NMR (CDC13, Me4Si) 6 0.96 (t, J = 7.4 Hz, 3 H), 1.55-1.7 (m, 2 H), 2.00 (d, J = 7.4 Hz, 3 H), 2.5-2.65 (m, 2 H), 5.46 (q, J = 7.4 Hz, 1 H), 7.3-7.55 (m. 5 H); I3C NMR (CDC13) 6 11.77, 14.19, 23.32, 26.88, 107.93, 126.23, 128.45 (2C), 128.74, 129.99, 149.84, 151.07, 169.18; IR (neat) 1756 cm-l; highresolution MS calcd for C15H1602228.1151, found 228.1156. (d)(Z)-2-Phenyl-J-(n-propyl)-4-benzylidene-2-buten-4-olide (12d). Using method D, 12d was formed in 68% NMR yield. Chromatography on silica gel (97/3 pentaneEt20) afforded 91 mg (63%) of 12d: stereoisomeric purity '98%; 'H NMR (CDCl3, Me4Si) 6 1.03 (t. J = 7.4 Hz, 3 H), 1.6-1.8 (m, 2 H), 2.65-2.75 (m, 2 H), 6.16 (s, 1 H), 7.3-7.6 (m, 8 H), 7.85 (d, J = 7.4 Hz, 2 H); I3C NMR (CDC13)6 14.31, 23.51, 27.00, 110.07, 125.97, 128.63, 128.69, 128.78 (2C), 128.87, 130.01, 130.55, 133.12, 148.16, 152.46, 169.24; IR (neat) 1758 cm-I; high-resolutionMS calcd for C2d31802 290.1307, found 290.1315. (e) (Z)-2,3-Dimethyl-4-otylidene-2-buten-4-olide (12e). Using method D, 12e was formed in 84% NMR yield. Chromatography on silica gel (99/1 pentane/EtzO) afforded 89 mg (80%) of 12e: stereoisomeric purity '98%; 'H NMR (CDCl3, Me4Si) 6 0.88 (t, J = 6.6 Hz, 3 H), 1.2-1.5 (m, 10 H), 1.89 (s, 3 H), 2.03 (s, 3 H), 2.3-2.45 (m, 2 H), 5.25 (t, J = 7.9 Hz, 1 H); 13CNMR (CDC13) 6 8.47, 9.67, 13.99, 22.54, 25.91, 28.98, 29.17 (2C), 31.69, 110.91, 123.85, 146.82, 149.88, 170 91; IR (neat) 1768 cm-I; high-resolution MS calcd for C14H2202222.1621, found 222.1628. (f) (Z)-2,3-Dimethyl-4-pentylidene-2-buten-4-olide (120. Using method D, 12f was formed in 82% NMR yield. Chromatography on silica gel (99/1 pentaneEt20) afforded 108 mg (80%) of 12f stereoisomeric purity >98%, 'H NMR (CDC13, Me4Si) 6 0.92 (t, J = 6.9 Hz, 3 H), 1.2-1.55 (m, 4 H), 1.90 (s, 3 H), 2.03 (s, 3 H), 2.3-2.55 (m, 2 H), 5.22 (t, J = 7.9 Hz, 1 H); I3C NMR (CDC13) 6 8.44, 9.72, 13.69. 22.24, 25.56, 31.20, 110.80, 123.79, 146.81, 149.86, 170.84; IR (neat) 1766 cm-l; high-resolution MS calcd for CllH1602 180.1151, found 180.1149. (8) 2-(n-Butyl)-4-(n-propylidene)-2-buten-4-olide (12g). Using method D, 12g was formed in 80% NMR yield as an 81/19 UE mixture along with an 8% of 2-(n-butyl)-4-(n-propyl)-2-butenolide.The spectral data are as follows: 2-12g: 'H NMR (CD&, Me4Si) 6 0.95 (t, J = 7.2 Hz, 3 H), 1.08 (t, J = 7.2 Hz, 3 H), 1.3-1.8 (m, 4 H), 2.3-2.5 (m, 4 H), 5.15 (t, J = 6.2 Hz, 1 H), 6.97 (s, 1 H); I3C NMR (CDC13) 6 13.79, 13.83, 19.76,22.37,24.92,29.78, 115.40, 135.28, 137.00, 148.14, 170.94. The following signals were discemible for the E-isomer: 'H NMR (CDC13, Me4Si) 6 5.59 (t, J = 5.0 Hz, 1 H), 7.28 (s, 1 H); 13C NMR(CDCl3) 6 22.52,25.29, 116.28, 135.28, 137.00, 148.14, 170.94. Under the same conditions except that benzene was used in place of DMF, 12g was formed in 74% NMR yield as a 62/38 ZIE mixture along with a 9% of 2-(n-butyl)-4-(n-propyl)-2-butenolide. (h) (E)- and (Z)-4-Ethylidene-2-(-tolylmethyl)-2-buten-4-olide (12h). Using method D, 12h was formed in 69% NMR yield as a 75/25 ZIE mixture along with a 25% of (E)-2-@-tolylmethylene)-4ethyl-3-buten-4-olide(llh). Chromatography on silica gel (6/1 pentane/ EtzO) afforded 131 mg (51%) of 12h (3, 38.7 mg of 12h ( E ) , and 64.3 mg (25%) of llh. The spectral data for (Z)-12h are as follows: 'H NMR (CDC13, Me4Si) 6 1.91 (d, J = 7.4 Hz, 3 H), 2.33 (s, 3 H), 3.61 (s, 2 H), 5.15 (q, J = 7.4 Hz, 1 H), 6.79 (s, 1 H), 7.12 (s, 4 H); I3C NMR (CDC13) 6 11.67, 20.95, 31.04, 109.99, 128.66, 129.33, 133.08, 134.10, 136.31, 137.66, 149.09, 170.27; IR (neat) 1764 cm-'; high-resolution MS calcd for C14Hl402 214.0994, found 214.0995. (E)-12h:'H NMR (CDC13, Me&) 6 1.81 (d, J = 7.7 Hz, 3 H), 2.35 (s, 3 H), 3.64 (s, 2 H), 5.66 (q, J = 7.4 Hz, 1 H), 7.07 (s, 1 H), 7.14 (s, 4 H); I3C NMR (CDCl3) 6 11.67, 21.04, 31.37, 109.32, 128.79, 129.48, 133.34, 134.08, 134.33, 136.48, 149.19, 170.29; IR (neat) 1760 cm-'. llh: 'H NMR (CDCl3, Me4Si) 6 1.24 (t, J = 7.4 Hz, 3 H), 2.39 (s, 3 H), 2.51 (q, J = 7.4 Hz, 2 H), 6.25 (s, 1 H), 7.23 (d, J = 8.0 Hz, 2 H), 7.28 ( s , 1 H), 7.45 (d, J = 8.0 Hz, 2 H); I3C NMR (CDCl3) 6 10.16,21.50, 22.15, 100.23, 129.70, 129.90, 132.30, 134.18, 140.49, 162.80, 170.07; IR (neat) 1768 cm-'.
J. Am. Chem. SOC.,Vol. 117, No. 12, 1995 3431 Pd-CatalyzedCarbonylation of /34odoenones Producing Butenolide Dimers. (a) 1,l'-Bis(-tolyl)-3,3'-dioxo-l,l'-bis(1H,1'H-isobenzofuran)(18). Using method C where 4 equiv of H20 (18 pL, 18 mg, 1.0 mmol) was used, 18 was formed in 95% NMR yield. Chromatography on silica gel (95/5 pentane/ethyl acetate) afforded 190 mg (85%) of 18 as a 1.2:l mixture of two diastereomers. The following signals correspond to the mixture of diastereomers denoted as a and b: IH NMR (CDC13, Me&) 6 2.14" (s, 6 H), 2.23b (s, 6 H), 6.90a (d, J = 8.1 H Z , ~ H ) , ~ . O ~ 8.1 ~ ( Hz,4H),7.2-7.8 ~,J= (m,20H),7.88b(d, J = 7.8 Hz, 2 H), 8.32a (d, J = 7.8 Hz, 2 H); I3C NMR (CDC13, Me4Si) 6 20.84,20.92,90.21,90.92, 124.36, 125.02, 125.50, 125.56, 126.18, 126.69, 128.46, 128.77, 129.53, 129.58, 134.06, 134.44, 138.04, 138.23, 149.34, 149.38, 168.83, 169.35; IR (CC4) 1778 cm-l; high-resolution MS calcd for C3&204 (M 1) 447.1596, found 447.1597. (b) 2,2'-Diphenyl-3,3',4,4'-tetra-(n-propyl)-5,S-dioxo-2,~-bis(W,W'-furan) (164. Using method C where NEt3 was replaced with KzC03 (140 mg, 1.0 mmol), 13d was formed in
