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See also: Barbero, A.; Cuadrado, P.; González, A. M.; Pulido, F. J.; Rubio, R.; Fleming, I. Tetrahedron Lett. 1992, 33, 5841.
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32
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0141523283
-
-
note
-
Acyclic ketones as 8 are of lesser utility, giving mixtures of diastereomeric alcohols (ca. 1:1) which are difficult to separate, whereas benzopiranone 12 leads to dirty mixtures of stannylated phenols resulting from lactone cleavage.
-
-
-
-
33
-
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0141746402
-
-
note
-
We think that the high de observed in the RLi additions to 13 is not entirely due to the gem-dimethyl group but also due to the tin-effect. In fact, destannylation of 13 (HI/THF, room temperature) followed by Meli addition renders a lower stereoselectivity, now yielding mixtures of diastereomeric alcohols (ratio ca. 5.5:1), the major alcohol being the one with the expected syn (OH/gem-dimethyl) stereochemistry.
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-
-
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34
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0003417469
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Trost, B., Fleming, I., Eds.; Pergamon, Elmsford, NY
-
It could be pointed out that torsional strain and steric factors developing in a transition state for 1,2-addition to ketones 9 and 10 would favor an equatorial (or pseudoequatorial) attack of the organolithium reagent leading to the observed stereochemistry; however, the extremely high diastereo-selectivity found with organolithium compounds is not consistent with literature data. In general, for substituted cyclopentanones, poor selectivities are reported (Comprehensive Organic Synthesis; Trost, B., Fleming, I., Eds.; Pergamon, Elmsford, NY, 1991; Vol. 1), and even 3-tert-butylcyclohexanone, which probably is sterically more demanding than the 3-alkenyl-stannane derivative 10, reacts with MeLi giving only a 78:22(cis:trans) ratio (Rei, M. H. J. Org. Chem. 1979. 44, 2760).
-
(1991)
Comprehensive Organic Synthesis
, vol.1
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-
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35
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0141634393
-
-
It could be pointed out that torsional strain and steric factors developing in a transition state for 1,2-addition to ketones 9 and 10 would favor an equatorial (or pseudoequatorial) attack of the organolithium reagent leading to the observed stereochemistry; however, the extremely high diastereo-selectivity found with organolithium compounds is not consistent with literature data. In general, for substituted cyclopentanones, poor selectivities are reported (Comprehensive Organic Synthesis; Trost, B., Fleming, I., Eds.; Pergamon, Elmsford, NY, 1991; Vol. 1), and even 3-tert-butylcyclohexanone, which probably is sterically more demanding than the 3-alkenyl-stannane derivative 10, reacts with MeLi giving only a 78:22(cis:trans) ratio (Rei, M. H. J. Org. Chem. 1979. 44, 2760).
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(1979)
J. Org. Chem.
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, pp. 2760
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-
Rei, M.H.1
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36
-
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0141634396
-
-
note
-
Crystallographic data for the structure reported have been deposited in the Cambridge Crystallographic Data Centre, ref. no. CCDC-139911. Copies of the data can be obtained from the CCDC. 12 Union Road, Cambridge CB21EZ, UK (fax: (+44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
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38
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0004133516
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Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma. K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, revision A.7; Gaussian, Inc.: Pittsburgh, PA, 1998. Theoretical level: MP2(fc)/3-21G*//HF/3-21G*.
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Cheeseman, J.R.6
Zakrzewski, V.G.7
Montgomery J.A., Jr.8
Stratmann, R.E.9
Burant, J.C.10
Dapprich, S.11
Millam, J.M.12
Daniels, A.D.13
Kudin, K.N.14
Strain, M.C.15
Farkas, O.16
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Mennucci, B.21
Pomelli, C.22
Adamo, C.23
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Ayala, P.Y.27
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Morokuma, K.29
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Rabuck, A.D.31
Raghavachari, K.32
Foresman, J.B.33
Cioslowski, J.34
Ortiz, J.V.35
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Liu, G.37
Liashenko, A.38
Piskorz, P.39
Komaromi, I.40
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Fox, D.J.43
Keith, T.44
Al-Laham, M.A.45
Peng, C.Y.46
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Gonzalez, C.48
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Johnson, B.G.51
Chen, W.52
Wong, M.W.53
Andres, J.L.54
Head-Gordon, M.55
Replogle, E.S.56
Pople, J.A.57
more..
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39
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0141634394
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note
-
w(C) = 1.7 Å.
-
-
-
-
42
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0000212392
-
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(c) Lipshutz, B. H.; Ellsworth, E. L.; Dimock, S. H.; Reuter, D. C. Tetrahedron Lett. 1989, 30, 2065.
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84922377851
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50
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(a) Oehlschlager, A. C.; Hutzinger, M. W.; Aksela, R.; Sharma, S.; Singh, S. M. Tetrahedron Lett. 1990, 31, 165.
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Singh, S.M.5
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51
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0000404899
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Lipshutz, B.H.7
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