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b) C. J. Elsevier, J. Meijer, G. Tadema, P. M. Stehouwer, H. J. T. Bos, P. Vermeer, J. Org. Chem. 1982, 47, 2194-2196;
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J. Org. Chem
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Elsevier, C.J.1
Meijer, J.2
Tadema, G.3
Stehouwer, P.M.4
Bos, H.J.T.5
Vermeer, P.6
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61
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0003066306
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c) C. J. Elsevier, P. Vermeer, A. Gedanken, W. Runge, J. Org. Chem. 1985, 50, 364-367.
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(1985)
J. Org. Chem
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, pp. 364-367
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Elsevier, C.J.1
Vermeer, P.2
Gedanken, A.3
Runge, W.4
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62
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0035850282
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J.-Y. Winum, L. Toupet, V. Barragan, G. Dewynter, J.-L. Montera, Org. Lett. 2001, 3, 2241-2243.
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(2001)
Org. Lett
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, pp. 2241-2243
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Winum, J.-Y.1
Toupet, L.2
Barragan, V.3
Dewynter, G.4
Montera, J.-L.5
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64
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34250667600
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-
For synthesis of the propargyl alcohol (±)-7e, see the Supporting Information.
-
For synthesis of the propargyl alcohol (±)-7e, see the Supporting Information.
-
-
-
-
65
-
-
34250638716
-
-
3OD. Therefore, it is apparent that the isomer 11a is thermodynamically more stable than the isomer 16a. At the present stage of our understanding, preferential formation of the relatively unstable isomer 16a by the reaction with TBAF/THF over the isomer 11a is unclear.
-
3OD. Therefore, it is apparent that the isomer 11a is thermodynamically more stable than the isomer 16a. At the present stage of our understanding, preferential formation of the relatively unstable isomer 16a by the reaction with TBAF/THF over the isomer 11a is unclear.
-
-
-
-
66
-
-
34250656624
-
-
Structure of trans-12e and cis-12e′ were determined by comparison of / values of the ring protons, as shown below. Figure presented
-
Structure of trans-12e and cis-12e′ were determined by comparison of / values of the ring protons, as shown below. Figure presented
-
-
-
-
67
-
-
34250645011
-
-
The structure of 11i was determined by NOE analysis. Figure presented
-
The structure of 11i was determined by NOE analysis. Figure presented
-
-
-
-
68
-
-
34250619249
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The phenyl group of 9i promotes the regioselective cyclization onto the central allenic carbon, presumably through a highly conjugated anionic transition state A and/or intermediate B. Figure presented
-
The phenyl group of 9i promotes the regioselective cyclization onto the central allenic carbon, presumably through a highly conjugated anionic transition state A and/or intermediate B. Figure presented
-
-
-
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69
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-
34250628085
-
-
Formation of the alkyne 18i can be rationalized by addition-elimination mechanism. One plausible pathway is shown below.
-
Formation of the alkyne 18i can be rationalized by addition-elimination mechanism. One plausible pathway is shown below.
-
-
-
-
70
-
-
34250639498
-
-
A similar result was obtained by the cyclization in the presence of palladium0, although the yield was lower, as shown below
-
A similar result was obtained by the cyclization in the presence of palladium(0), although the yield was lower, as shown below.
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-
-
-
71
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0028150852
-
-
Related five-membered ring formations by intramolecular amination of carbon-carbon triple bond have been already reported, see: a Y. Tamaru, M. Kimura, S. Tanaka, S. Kure, Z. Yoshida, Bull. Chem. Soc. Jpn. 1994, 67, 2838-2849;
-
Related five-membered ring formations by intramolecular amination of carbon-carbon triple bond have been already reported, see: a) Y. Tamaru, M. Kimura, S. Tanaka, S. Kure, Z. Yoshida, Bull. Chem. Soc. Jpn. 1994, 67, 2838-2849;
-
-
-
-
72
-
-
0030017870
-
Figure presented
-
b) P. A. Jacobi, H. L. Brielmann, S. I. Hauck, Figure presented J. Org. Chem. 1996, 61, 5013-5023;
-
(1996)
J. Org. Chem
, vol.61
, pp. 5013-5023
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Jacobi, P.A.1
Brielmann, H.L.2
Hauck, S.I.3
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73
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0033597241
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-
c) M. M. Cid, D. Domínguez, L. Castedo, E. M. Vázquez- López, Tetrahedron 1999, 55, 5599-5610.
-
(1999)
Tetrahedron
, vol.55
, pp. 5599-5610
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Cid, M.M.1
Domínguez, D.2
Castedo, L.3
Vázquez- López, E.M.4
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74
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34250617963
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-
Isolation of 20′b was extremely difficult due to the hydrolysis during purification, yielding a ring-opening product 23 b. Accordingly, 23b was isolated in 70% yield after acidic workup and fully characterized.
-
Isolation of 20′b was extremely difficult due to the hydrolysis during purification, yielding a ring-opening product 23 b. Accordingly, 23b was isolated in 70% yield after acidic workup and fully characterized.
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-
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75
-
-
34250661137
-
-
1NMR analysis of which showed formation of 20′b and 21b (2.5:1) quantitatively, without detecting 23b.
-
1NMR analysis of which showed formation of 20′b and 21b (2.5:1) quantitatively, without detecting 23b.
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-
-
-
76
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-
34250687975
-
-
To reveal the intermediate of this tandem cyclization reaction, we investigated stepwise reaction of the bromoallene 24. Treatment of the bromoallene 24 with NaH in DMF gave piperidine 78 in 79% yield. Reaction of 78 under the same reaction conditions as the one-pot reaction afforded the exo-cyclized product 29 (93 %) as a single isomer.
-
To reveal the intermediate of this tandem cyclization reaction, we investigated stepwise reaction of the bromoallene 24. Treatment of the bromoallene 24 with NaH in DMF gave piperidine 78 in 79% yield. Reaction of 78 under the same reaction conditions as the one-pot reaction afforded the exo-cyclized product 29 (93 %) as a single isomer.
-
-
-
-
77
-
-
34250613139
-
-
Structure of (±)-32 was confirmed by NOE analysis as shown below. Figure presented
-
Structure of (±)-32 was confirmed by NOE analysis as shown below. Figure presented
-
-
-
-
78
-
-
34250628502
-
-
The reaction of 27 with NaH in MeOH afforded an inseparable mixture of (E)- and (Z)-enynes, produced by elimination of HBr under the basic reaction conditions.
-
The reaction of 27 with NaH in MeOH afforded an inseparable mixture of (E)- and (Z)-enynes, produced by elimination of HBr under the basic reaction conditions.
-
-
-
-
79
-
-
34250636369
-
-
1H NMR spectroscopy.
-
1H NMR spectroscopy.
-
-
-
-
80
-
-
34250649770
-
-
4] was ineffective: only 15% of the cyclosulfamide 49 and a trace amount of 32, produced by the uncatalyzed reaction (Table 5), were obtained.
-
4] was ineffective: only 15% of the cyclosulfamide 49 and a trace amount of 32, produced by the uncatalyzed reaction (Table 5), were obtained.
-
-
-
-
81
-
-
34250681437
-
-
Without treatment with HC1, the ratio of regioisomers (products of the type 53 and 54) is variable.
-
Without treatment with HC1, the ratio of regioisomers (products of the type 53 and 54) is variable.
-
-
-
-
82
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34250646677
-
-
The palladium-catalyzed cyclization of bromoallene 79 having a six-atom tether between the sulfamide and allenyl group gave a trace of the desired tricyclic sulfamide 80 containing a nine-membered ring (<5% yield). Figure presented
-
The palladium-catalyzed cyclization of bromoallene 79 having a six-atom tether between the sulfamide and allenyl group gave a trace of the desired tricyclic sulfamide 80 containing a nine-membered ring (<5% yield). Figure presented
-
-
-
-
83
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34250682668
-
-
Treatment of bromoallene 65 with NaOMe in DMF gave azetidine 81 as a major product and a small amount of dihydropyrrole 67 having a methoxymethyl group. We have already reported the formation of azetidines by NaH-mediated intramolecular amination of bromoallenes: see. reference [13b, Figure presented
-
Treatment of bromoallene 65 with NaOMe in DMF gave azetidine 81 as a major product and a small amount of dihydropyrrole 67 having a methoxymethyl group. We have already reported the formation of azetidines by NaH-mediated intramolecular amination of bromoallenes: see. reference [13b]. Figure presented
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-
-
-
84
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0002538829
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a) S. Ogoshi, K. Tsutsumi, S. Nishiguchi, H. Kurosawa, J. Organomet, Chem. 1995, 493, C19-C21;
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(1995)
J. Organomet, Chem
, vol.493
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Ogoshi, S.1
Tsutsumi, K.2
Nishiguchi, S.3
Kurosawa, H.4
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85
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0032481580
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b) K. Tsutsumi, S. Ogoshi, S. Nishiguchi, H. Kurosawa, J. Am. Chem. Soc. 1998, 120, 1938-1939;
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(1998)
J. Am. Chem. Soc
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, pp. 1938-1939
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Tsutsumi, K.1
Ogoshi, S.2
Nishiguchi, S.3
Kurosawa, H.4
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86
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0033459584
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c) K. Tsutsumi, T. Kawase, K. Kakiuchi, S. Ogoshi, Y. Okada, H. Kurosawa, Bull. Chem. Soc. Jpn. 1999, 72, 2687-2692;
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Bull. Chem. Soc. Jpn
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, pp. 2687-2692
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Tsutsumi, K.1
Kawase, T.2
Kakiuchi, K.3
Ogoshi, S.4
Okada, Y.5
Kurosawa, H.6
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88
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0032481404
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In the reaction of propargylic carbonates, it is proposed that the first nucleophilic addition onto the η3-propargylpalladium produces a metallacyclobutene, protonation of which generates the η3- allylpalla- dium complex: C. P. Casey, J. R. Nash, C. S. Yi, A. D. Selmeczy, S. Chung, D. R. Powell, R. K. Hayashi, J. Am. Chem. Soc. 1998, 120, 722-733
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3- allylpalla- dium complex: C. P. Casey, J. R. Nash, C. S. Yi, A. D. Selmeczy, S. Chung, D. R. Powell, R. K. Hayashi, J. Am. Chem. Soc. 1998, 120, 722-733.
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