Palladium-catalyzed regioselective bis-alkynylation of propargylic carbonates: Synthesis of enediyne compounds

Tetrahedron Letters

Volumn 38, Issue 35, 1997, Pages 6241-6244

  Hayashi, Minoru ^a   Saigo, Kazuhiko ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENYLDIALKYNE DERIVATIVE; ALKYNE; CARBONIC ACID DERIVATIVE; PALLADIUM COMPLEX; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL REACTION; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0030810935     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)01435-4     Document Type: Article

References (28)

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12. In the course of optimization of the reaction conditions, an obvious solvent effect was observed. Solvents with relatively high polarity tended to accelerate the reaction, giving the allenyne. Dimethoxyethane (DME) was the solvent of choice, and THF could be used even though the yield was slightly lower. In polar solvents such as DMSO and acetonitrile, the formation of the allenyne completed very fast even at rt, but the enediyne product was formed in lower yield even at 80 °C.
13. 3) for the products: 2a (E): δ 0.12 (s, 9 H), 0.21 (s, 9 H), 1.15-1.23 (m, 1 H), 1.40-1.50 (m, 1 H), 2.05 (s, 3 H), 2.14-2.28 (m, 1 H), 2.45-2.52 (m, 1 H), 7.04-7.30 (m, 5 H); 2b (E): δ 2.21 (s, 6 H), 7.25-7.52 (m, 10 H); 2b (Z): δ 2.02 (s, 6 H), 7.25-7.52 (m, 10 H); 2c (E): δ 1.23 (t, J = 7.5 Hz, 3 H), 2.22 (s, 3 H), 2.61 (q, J = 7.5 Hz, 2 H), 7.28-7.55 (m, 10 H); 2c (Z): δ 1.20 (t, J = 7.5 Hz, 3 H), 2.03 (s, 3 H), 2.36 (q, J = 7.5 Hz, 2 H), 7.18-7.56 (m, 10 H); 2d (E): δ 0.92 (t, J = 7.2 Hz, 6 H), 1.07 (t, J = 7.5 Hz, 3 H), 1.37-1.65 (m, 8 H), 1.98 (s, 3 H), 2.30-2.48 (m, 6 H); 2d (Z): δ 0.92 (t, J = 6.9 Hz, 6 H), 1.06 (t, J = 7.5 Hz, 3 H), 1.39-1.62 (m, 8 H), 1.85 (s, 3 H), 2.17 (q, J= 7.5 Hz, 2 H), 2.35-2.44 (m, 4 H); 2e (E): 8 0.19 (s, 9 H), 0.20 (s, 9 H), 1.09 (t, J = 7.5 Hz, 3 H), 2.01 (s, 3 H), 2.40 (q, J = 7.5 Hz, 2 H); 2e (Z): δ 0.21 (s, 18 H), 1.08 (t, J = 7.5 Hz, 3 H), 1.87 (s, 3 H), 2.19 (q, J = 7.5 Hz, 2 H); 2f (E): 8 1.08 (t, J = 7.5 Hz, 3 H), 1.45-1.95 (m, 12 H), 2.02 (s, 3 H), 2.40 (q, J = 7.5 Hz, 2 H), 3.48-3.62 (m, 2 H), 3.80-3.93 (m, 2 H), 4.45 (s, 2 H), 4.48 (s, 2 H), 4.80-4.92 (m, 2 H); 2f (Z): δ 1.08 (t, J = 7.5 Hz, 3 H), 1.45-1.85 (m, 12 H), 1.88 (s, 3 H), 2.22 (q, J = 7.5 Hz, 2 H), 3.48-3.62 (m, 2 H), 3.77-3.93 (m, 2 H), 4.45 (s, 2 H), 4.47 (s, 2 H), 4.88-4.95 (m, 2 H); 3c: δ 1.74 (quintet, J = 7.5 Hz, 2 H), 2.10 (dq, J = 3.5, 7.5 Hz, 2 H), 3.51 (t, J = 6.4 Hz, 2 H), 4.51 (s, 2 H), 4.66 (dt, J = 3.5, 6.4 Hz, 2 H), 5.11 (quintet, J = 6.7 Hz, 1 H), 7.22-7.38 (m, 5 H); 4 (E): δ 0.94 (t, J = 6.5 Hz, 3 H), 1.14 (t, J = 8.2 Hz, 3 H), 1.35-1.65 (m, 4 H), 2.10 (s, 3 H), 2.30-2.56 (m, 4 H), 7.17-7.50 (m, 5 H); 4 (Z): δ 0.86 (t, J =6.9 Hz, 3H), 1.11 (t, J = 7.5 Hz, 3 H), 1.38-1.64 (m, 4 H), 1.96 (s, 3 H), 2.24 (q, J = 7.5 Hz, 2 H), 2.43 (t, J = 6.9 Hz, 2 H), 7.15-7.60 (m, 5 H). All products gave the corresponding molecular ion peaks in their mass spectra.
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16. The low yield of the allenyne would be attributable to its instability. It was reported that no stable coupling product could be isolated from a propargylic carbonate without any substituent at the propargylic position, see: (a) Mandai, T.; Nakata, T.; Murayama, H.; Yamaoki, H.; Ogawa, M.; Kawada, M.; Tsuji, J. Tetrahedron Lett. 1990, 31, 7179. (b) Mandai, T.; Murayama, H.; Nakata, T.; Yamaoki, H.; Ogawa, M.; Kawada, M.; Tsuji, J. J. Organometal. Chem. 1991, 417, 305.
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22. The palladium-catalyzed alkynylation of an allene so far reported gave a conjugated enyne, see: Trost, B. M.; Kottirsch, G. J. Am. Chem. Soc. 1990, 112, 2816.
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