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Recently, the revised structure of this natural compound has been reported:;;;; J. Nat. Prod. 2010, 73, 279-283
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Gerwick, W. H.; Roberts, M. A.; Proteau, P. J.; Chen, J. L. J. Appl. Phycol. 1994, 6, 143-149 Recently, the revised structure of this natural compound has been reported: Pereira, A. R.; Byrum, T.; Shibuya, G. M.; Vanderwal, C. D.; Gerwick, W. H. J. Nat. Prod. 2010, 73, 279-283
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19
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51949102215
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An elegant methodology was developed by this group
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An elegant methodology was developed by this group: Shibuya, G. M.; Kanady, J. S.; Vanderwal, C. D. J. Am. Chem. Soc. 2008, 130, 12514-12518
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While the present paper was in review, asymmetric total synthesis of malhamensilipine A was reported:;;;; J. Am. Chem. Soc. 2010, 132, 2542-2543
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Kanady, J. S.; Nguyen, J. D.; Ziller, J. W.; Vanderwal, C. D. J. Org. Chem. 2009, 74, 2175-2178 While the present paper was in review, asymmetric total synthesis of malhamensilipine A was reported: Bedke, D. K.; Shibuya, G. M.; Pereira, A. R.; Gerwick, W. H.; Vanderwal, C. D. J. Am. Chem. Soc. 2010, 132, 2542-2543
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59049083939
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For the total synthesis of (±)-hexachlorosulfolipid, see:;;, For an account of this work, see:; Nature 2009, 457, 548-549 For related studies, see:;;; J. Am. Chem. Soc. 2009, 131, 15866-15876
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For the total synthesis of (±)-hexachlorosulfolipid, see: Nilewski, C.; Geisser, R. W.; Carreira, E. M. Nature 2009, 457, 573-576 For an account of this work, see: Bedke, D. K.; Vanderwal, C. D. Nature 2009, 457, 548-549 For related studies, see: Nilewski, C.; Geisser, R. W.; Ebert, M.-O.; Carreira, E. M. J. Am. Chem. Soc. 2009, 131, 15866-15876
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For a pertinent review on the chemistry of allylic 1,3-strain, see
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For a pertinent review on the chemistry of allylic 1,3-strain, see: Hoffmann, R. W. Chem. Rev. 1989, 89, 1841-1860
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Chamberlin and co-workers (ref 10a) have reported that 2-iodo-1,3- anti -diols are stereo- and regioselectively produced from 1,2-disubstituted allylic alcohols via an intermediacy of cyclic iodonium ions generated preferentially syn to the allylic hydroxyl group in the 1,3-allylic strain model, followed by their nucleophilic hydration at the sterically more accessible position. This observation suggested that dichlorination of our allylic alcohol substrate 5 would favor the production of undesired (2 S, 3 R)-pentachloride 21
-
Chamberlin and co-workers (ref 10a) have reported that 2-iodo-1,3- anti -diols are stereo- and regioselectively produced from 1,2-disubstituted allylic alcohols via an intermediacy of cyclic iodonium ions generated preferentially syn to the allylic hydroxyl group in the 1,3-allylic strain model, followed by their nucleophilic hydration at the sterically more accessible position. This observation suggested that dichlorination of our allylic alcohol substrate 5 would favor the production of undesired (2 S, 3 R)-pentachloride 21. Chamberlin, A. R.; Mulholland, R. L., Jr. Tetrahedron 1984, 40, 2297-2302
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0021097053
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Other related studies on the diastereoselective halogenation of allylic alcohols, for instance:; J. Org. Chem. 1981, 46, 1227-1229
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Chamberlin, A. R.; Dezube, M.; Dussault, P.; McMills, M. C. J. Am. Chem. Soc. 1983, 105, 5819-5825 Other related studies on the diastereoselective halogenation of allylic alcohols, for instance: Midland, M. M.; Halterman, R. L. J. Org. Chem. 1981, 46, 1227-1229
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Liotta, D.; Zima, G.; Saindane, M. J. Org. Chem. 1982, 47, 1258-1267
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Morrison J.D., Ed.; Academic Press, Inc.: New York
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Bartlett, P. A. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press, Inc.: New York, 1984; Vol. 3, pp 411 - 454.
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Bartlett, P.A.1
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Kim, K. S.; Park, H. B.; Kim, J. Y.; Ahn, Y. H.; Jeong, I. H. Tetrahedron Lett. 1996, 37, 1249-1252
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31
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33646465280
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Allylic alcohol 10 was prepared by a four-step protocol similar to the known method; see
-
Allylic alcohol 10 was prepared by a four-step protocol similar to the known method; see: Lu, K.; Huang, M.; Xiang, Z.; Liu, Y.; Chen, J.; Yang, Z. Org. Lett. 2006, 8, 1193-1196
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Lu, K.1
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84941216140
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For reviews, see J. D., Ed.; Academic Press: Orlando
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For reviews, see: Finn, M. G.; Sharpless, K. B. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: Orlando, 1985; Vol. 5, p 247 - 308.
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Finn, M.G.1
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Trost, B. M.; Fleming, I., Eds.; Pergamon Press: Oxford
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Johnson, R. A.; Sharpless, K. B. In Comprehensive Organic Synthesis; Trost, B. M.; Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 7, pp 389 - 436.
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Johnson, R.A.1
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51
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0542376714
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The stereochemistry of dichloride 11 was established by its transformation into (E)-olefin by means of the known reductive olefination protocol.;, For details, see the Supporting Information
-
The stereochemistry of dichloride 11 was established by its transformation into (E)-olefin by means of the known reductive olefination protocol. Sonnet, P. E.; Oliver, J. E. J. Org. Chem. 1976, 41, 3284-3286 For details, see the Supporting Information.
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77955678774
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Selected reviews for Hosomi-Sakurai reactions Li, J. J., Ed.; John Wiley & Sons: Hoboken, NJ
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Selected reviews for Hosomi-Sakurai reactions: Biamonte, M. A. In Name Reactions for Homologations; Li, J. J., Ed.; John Wiley & Sons: Hoboken, NJ, 2009; Part 1, pp 539 - 575.
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Name Reactions for Homologations
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45249121299
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Yamamoto, H.; Ishihara, K., Eds.; Wiley-VCH Verlag GmbH & Co. KGaA: Weinhem
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Hosomi, A.; Miura, K. In Acid Catalysis in Modern Organic Synthesis; Yamamoto, H.; Ishihara, K., Eds.; Wiley-VCH Verlag GmbH & Co. KGaA: Weinhem, 2008; Vol. 1, pp 469 - 516.
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Trost, B. M.; Fleming, I., Eds.; Pergamon Press: Oxford
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Fleming, I. In Comprehensive Organic Synthesis; Trost, B. M.; Fleming, I., Eds.; Pergamon Press: Oxford, 1991; vol. 6, pp 563 - 593.
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33644959351
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For a theoretical investigation of the nucleophilic addition to α-chloroaldehydes, see:;;, For a recent example, see:; Org. Lett. 2007, 9, 5083-5086 and references cited therein
-
For a theoretical investigation of the nucleophilic addition to α-chloroaldehydes, see: Cee, V. J.; Cramer, C. J.; Evans, D. A. J. Am. Chem. Soc. 2006, 128, 2920-2930 For a recent example, see: Kang, B.; Britton, R. Org. Lett. 2007, 9, 5083-5086 and references cited therein
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Britton, R.5
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62
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77955698894
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1H NMR spectra
-
1H NMR spectra.
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-
-
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63
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77955694249
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-
3P/hexachloroacetone similarly gave desired trichloride 6 in 74% yield. However, partly because side reactions occurred under this condition, the yields varied when the reactions were performed on a large scale
-
3P/hexachloroacetone similarly gave desired trichloride 6 in 74% yield. However, partly because side reactions occurred under this condition, the yields varied when the reactions were performed on a large scale.
-
-
-
-
64
-
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77955692458
-
-
In this case, dichloroethane was used as solvent because of the higher solubility of the reagents and substrate. Dichlorination of epoxide 12 in toluene, however, afforded trichloride 6 in a comparable yield (68%) to that in dichloroethane
-
In this case, dichloroethane was used as solvent because of the higher solubility of the reagents and substrate. Dichlorination of epoxide 12 in toluene, however, afforded trichloride 6 in a comparable yield (68%) to that in dichloroethane.
-
-
-
-
65
-
-
77955680762
-
-
This material was readily prepared by silylating 5-hexen-1-ol with TBDPSCl in the presence of imidazole in DMF (95% yield)
-
This material was readily prepared by silylating 5-hexen-1-ol with TBDPSCl in the presence of imidazole in DMF (95% yield).
-
-
-
-
66
-
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0037151671
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Winkler, J. D.; Rouse, M. B.; Greaney, M. F.; Harrison, S. J.; Jeon, Y. T. J. Am. Chem. Soc. 2002, 124, 9726-9728
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Winkler, J.D.1
Rouse, M.B.2
Greaney, M.F.3
Harrison, S.J.4
Jeon, Y.T.5
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67
-
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77955685406
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-
The stereochemistry of β-alcohol 13a and α-alcohol 13b was determined by their transformation into the corresponding cis - and trans -epoxides, respectively. For details, see the Supporting Information
-
The stereochemistry of β-alcohol 13a and α-alcohol 13b was determined by their transformation into the corresponding cis-and trans -epoxides, respectively. For details, see the Supporting Information.
-
-
-
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68
-
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0031592567
-
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3) dichlorination protocols have nearly identical levels of efficiency and selectivity. However, we assume that there may be some differences in the Lewis acidities of the two reagent systems, which possibly arise from the chemical species generated in the reaction mixtures
-
3) dichlorination protocols have nearly identical levels of efficiency and selectivity. However, we assume that there may be some differences in the Lewis acidities of the two reagent systems, which possibly arise from the chemical species generated in the reaction mixtures. Markó, I. E.; Richardson, P. R.; Bailey, M.; Maguire, A. R.; Coughlan, N. Tetrahedron Lett. 1997, 38, 2339-2342
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Markó, I.E.1
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69
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0030722873
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Schlama, T.; Gabriel, K.; Gouverneur, V.; Mioskowski, C. Angew. Chem., Int. Ed. Engl. 1997, 36, 2342-2344
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Schlama, T.1
Gabriel, K.2
Gouverneur, V.3
Mioskowski, C.4
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70
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77955689300
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Compound 19 was possibly produced by the neighboring participation of the trichloroacetyl group followed by the elimination. Its stereochemistry at the 3 position has, however, yet to be determined
-
Compound 19 was possibly produced by the neighboring participation of the trichloroacetyl group followed by the elimination. Its stereochemistry at the 3 position has, however, yet to be determined.
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-
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71
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77955677868
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Conformational analysis on simple hydrocarbon models having a shorter backbone was carried out using the Gaussian 03 program [B3LYP/6-31G(d)]. For experimental details, see the Supporting Information. ;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;; ; Gaussian 03, Revision E.01; Gaussian, Inc.: Wallingford, CT
-
Conformational analysis on simple hydrocarbon models having a shorter backbone was carried out using the Gaussian 03 program [B3LYP/6-31G(d)]. For experimental details, see the Supporting Information. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada., M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Revision E.01; Gaussian, Inc.: Wallingford, CT, 2004.
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Frisch, M.J.1
Trucks, G.W.2
Schlegel, H.B.3
Scuseria, G.E.4
Robb, M.A.5
Cheeseman, J.R.6
Montgomery, J.A.7
Vreven, T.8
Kudin, K.N.9
Burant, J.C.10
Millam, J.M.11
Iyengar, S.S.12
Tomasi, J.13
Barone, V.14
Mennucci, B.15
Cossi, M.16
Scalmani, G.17
Rega, N.18
Petersson, G.A.19
Nakatsuji, H.20
Hada, M.21
Ehara, M.22
Toyota, K.23
Fukuda, R.24
Hasegawa, J.25
Ishida, M.26
Nakajima, T.27
Honda, Y.28
Kitao, O.29
Nakai, H.30
Klene, M.31
Li, X.32
Knox, J.E.33
Hratchian, H.P.34
Cross, J.B.35
Bakken, V.36
Adamo, C.37
Jaramillo, J.38
Gomperts, R.39
Stratmann, R.E.40
Yazyev, O.41
Austin, A.J.42
Cammi, R.43
Pomelli, C.44
Ochterski, J.W.45
Ayala, P.Y.46
Morokuma, K.47
Voth, G.A.48
Salvador, P.49
Dannenberg, J.J.50
Zakrzewski, V.G.51
Dapprich, S.52
Daniels, A.D.53
Strain, M.C.54
Farkas, O.55
Malick, D.K.56
Rabuck, A.D.57
Raghavachari, K.58
Foresman, J.B.59
Ortiz, J.V.60
Cui, Q.61
Baboul, A.G.62
Clifford, S.63
Cioslowski, J.64
Stefanov, B.B.65
Liu, G.66
Liashenko, A.67
Piskorz, P.68
Komaromi, I.69
Martin, R.L.70
Fox, D.J.71
Keith, T.72
Al-Laham, M.A.73
Peng, C.Y.74
Nanayakkara, A.75
Challacombe, M.76
Gill, P.M.77
Johnson, B.78
Chen, W.79
Wong, M.W.80
Gonzalez, C.81
Pople, J.A.82
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72
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77955706333
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We currently assume that the low energy gap observed between the two conformers a and b may arise from the relative instability of conformer a that suffers from steric interaction between the hydrogen atom at C3 position and the chlorine atom at C5. The interaction increases the relative energy of conformer a, leading to the proximity in the conformational energy gap of the two possible conformers
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We currently assume that the low energy gap observed between the two conformers a and b may arise from the relative instability of conformer a that suffers from steric interaction between the hydrogen atom at C3 position and the chlorine atom at C5. The interaction increases the relative energy of conformer a, leading to the proximity in the conformational energy gap of the two possible conformers.
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73
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77955670925
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In this case, however, the observed stereochemical outcome may possibly indicate an intermediacy of the coordination of a Lewis acidic reagent to the hydroxyl group, such as the trimethylsilylated manganese complex, (22) which prevents substrate 5 from forming a β-chloronium intermediate as in the case of substrate 14, eventually leading to (2 R, 3 S)-pentachloride 20 as the major product. We are currently making further efforts to elucidate the origin of this stereochemical preference
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In this case, however, the observed stereochemical outcome may possibly indicate an intermediacy of the coordination of a Lewis acidic reagent to the hydroxyl group, such as the trimethylsilylated manganese complex, (22) which prevents substrate 5 from forming a β-chloronium intermediate as in the case of substrate 14, eventually leading to (2 R, 3 S)-pentachloride 20 as the major product. We are currently making further efforts to elucidate the origin of this stereochemical preference.
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74
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33845373603
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Also see ref 5a
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Takai, K.; Nitta, K.; Utimoto, K. J. Am. Chem. Soc. 1986, 108, 7408-7410 Also see ref 5a.
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(1986)
J. Am. Chem. Soc.
, vol.108
, pp. 7408-7410
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Takai, K.1
Nitta, K.2
Utimoto, K.3
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