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0001140189
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For a recent and insightful perspective on. subsequent work
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For a recent and insightful perspective on. subsequent work, see: A. Eschenmoser, D. Arigoni, Helv. Chim. Acta 2005, 88 , 3011-3050.
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For a review, see: F. H. Vaillancourt, E. Yeh, D. A. Vosburg, S. Garneau-Tsodikova, C. T. Walsh, Chem Rev. 2006, 106, 3364-3378.
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7
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0024429564
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For the original isolation of these natural products
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For the original isolation of these natural products, see: a) M. E. Wall, M. C. Wani, G. Manikumar, H. Taylor, T. J. Hughes, K. Gaetano, W H. Gerwick, A. T. McPhail, D. R. McPhail, J. Nat Prod. 1989, 52, 1092-1099;
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Gerwick, W.H.7
Mcphail, A.T.8
Mcphail, D.R.9
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9
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0022637236
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In total, there are more than 135 bromine-containing natural products known, that possess the general six-membered ring carbon, framework shown below that could result from a bromonium-induced cation-it cyclization of an isoprene-derived starting material. Of these, many have potent biological activity, including antitumor, antibacterial, and anti-HIV activity
-
c) K. Shiomi, H. Nakamura, H. Iinuma, H. Naganawa, K. Isshiki, T. Tkkeuchi, H. Umezawa, Y. Iitaka, J. Antibiot. 1986, 39, 494-501. In total, there are more than 135 bromine-containing natural products known, that possess the general six-membered ring carbon, framework shown below that could result from a bromonium-induced cation-it cyclization of an isoprene-derived starting material. Of these, many have potent biological activity, including antitumor, antibacterial, and anti-HIV activity.
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J. Antibiot.
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Shiomi, K.1
Nakamura, H.2
Iinuma, H.3
Naganawa, H.4
Isshiki, K.5
Tkkeuchi, T.6
Umezawa, H.7
Iitaka, Y.8
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10
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0017767367
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-
For selected examples
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For selected examples, see: d) G. R. Pettit, C. L. Herald, M. S. Allen, R. B. Von Dreele, L. D. Vanell, J. P. Y Kao, W Blake, J. Am. Chem. Soc. 1977, 99, 262-263;
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Pettit, G.R.1
Herald, C.L.2
Allen, M.S.3
Von Dreele, R.B.4
Vanell, L.D.5
Kao, J.P.Y.6
Blake, W.7
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11
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70349696974
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e) S. Loya, M. Bakhanashvili, Y. Kashman, A. Hizi, Arch. Biochem. Biophys 1995, 316, 789796;
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Arch. Biochem. Biophys
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Loya, S.1
Bakhanashvili, M.2
Kashman, Y.3
Hizi, A.4
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53649102215
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f) C. S. Vairappan, M. Suzuki, T. Ishii, T. Okino, T. Abe, M. Masuda, Phytochemistry 2008, 69,2490-2494.
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Phytochemistry
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Vairappan, C.S.1
Suzuki, M.2
Ishii, T.3
Okino, T.4
Abe, T.5
Masuda, M.6
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13
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9344254411
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For biosynthetic studies with the snyderols and the napyradiomycins
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For biosynthetic studies with the snyderols and the napyradiomycins, see: a) J. N. Carter-Franklin, A. Butler, J. Am. Chem. Soc. 2004, 126, 15060-15066;
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J. Am. Chem. Soc.
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Carter-Franklin, J.N.1
Butler, A.2
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34447558011
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b) J. M. Winter, M. C. Moffitt, E. Zazopoulos, J. B. McAlpine, P. C. Dorrestein, B. S. Moore, J. Biol. Chem. 2007, 282,16362-16368.
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Winter, J.M.1
Moffitt, M.C.2
Zazopoulos, E.3
Mcalpine, J.B.4
Dorrestein, P.C.5
Moore, B.S.6
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15
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69949155630
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For a recent, asymmetric total synthesis of napyradiomycin Al
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For a recent, asymmetric total synthesis of napyradiomycin Al, see: c) S. A. Snyder, Z. Tang, R. Gupta, J. Am. Chem. Soc. 2009, 131, 5744-5745.
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J. Am. Chem. Soc.
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Snyder, S.A.1
Tang, Z.2
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b) T. Kato, I. Ichinose, A. Kamoshida, Y. Kitahara, J. Chem. Soc. Chem. Commun. 1976, 518-519;
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Kato, T.1
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c) A. G. González, J. D. Martín, C. Pérez, M. A. Ramírez, Tetrahedron Lett. 1976, 17, 137-138;
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González, A.G.1
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f) T. Kato, M. Mochizuki, T. Hirano, S. Fujiwara, T. Uyehara, J. Chem. Soc. Chem. Commun. 1984, 1077-1078;
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Kato, T.1
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g) Y. Yamaguchi, T. Uyehara, T. Kato, Tetrahedron Lett. 1985, 26, 343-346;
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Yamaguchi, Y.1
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h) S. Fujiwara, K. Takeda, T. Uyehara, T. Kato, Chem. Lett. 1986,1763-1766;
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Fujiwara, S.1
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i) A. Tanaka, M. Sato, K. Yamashita, Agric. Biol. Chem. 1990, 54, 121-123.
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Tanaka, A.1
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27
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0005990450
-
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A graphical summary of all of the bromonium-induced cyclizations in Refs. [6-8] can. be found at the end of the Supporting Information to provide a full sense of the true stateof-the-art in these reactions in racemic format
-
A. Tanaka, T. Oritani, Biosci. Biotechnol. Biochem. 1995, 59, 516-517. A graphical summary of all of the bromonium-induced cyclizations in Refs. [6-8] can. be found at the end of the Supporting Information to provide a full sense of the true stateof-the-art in these reactions in racemic format.
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Biosci. Biotechnol. Biochem.
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Tanaka, A.1
Oritani, T.2
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28
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33847218271
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It should be noted that this paper describes asymmetric iodoniuminduced cyclizations of three structurally similar geraniolderived substrates possessing electron-rich alkene nucleophiles; attempts to extend the developed system directly to bromine afforded products in poor enantiomeric excess, revealing that the problem of inducing asymmetry in this transformation is far from a trivial one; these challenges, of course, are in addition to those described for effecting bromonium-induced cyclizations in racemic format as already described
-
A. Sakakura, A. Ukai, K. Ishihara, Nature 2007, 445, 900-903. It should be noted that this paper describes asymmetric iodoniuminduced cyclizations of three structurally similar geraniolderived substrates possessing electron-rich alkene nucleophiles; attempts to extend the developed system directly to bromine afforded products in poor enantiomeric excess, revealing that the problem of inducing asymmetry in this transformation is far from a trivial one; these challenges, of course, are in addition to those described for effecting bromonium-induced cyclizations in racemic format as already described.
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(2007)
Nature
, vol.445
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Sakakura, A.1
Ukai, A.2
Ishihara, K.3
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29
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4243051318
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II-based cyclizations followed by bromine replacement
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II-based cyclizations followed by bromine replacement: a) E. A. Couladouros, V. P. Vidali, Chem. Eur. 2004, 10, 3822-3835;
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Chem. Eur.
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Couladouros, E.A.1
Vidali, V.P.2
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0006616419
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b) A. Murai, A. Abiko, T. Masamune, Tetrahedron Lett. 1.984, 25, 4955-4958;
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Murai, A.1
Abiko, A.2
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33
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84988189521
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Related reagents with different Lewis acidic counterions have been known for far longer, though again, their reactivity with olefins or other nucleophilies remains unreported
-
b) H. F. Askew, P. N. Gates, A. S. Muir, J. Raman Spectrosc 1991, 22, 265-274. Related reagents with different Lewis acidic counterions have been known for far longer, though again, their reactivity with olefins or other nucleophilies remains unreported:
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(1991)
J. Raman Spectrosc
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, pp. 265-274
-
-
Askew, H.F.1
Gates, P.N.2
Muir, A.S.3
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35
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84983921238
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d) R. Minkwitz, V. Gerhard, A. Werner, J. Anorg. Allg. Chem. 1989, 575, 137-144;
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Minkwitz, R.1
Gerhard, V.2
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37
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0031479259
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f) B. Regelmann, K.W. Klinkhammer, A. Schmidt, J. Anorg. Allg. Chem. 1997, 623, 1633-1638.
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J. Anorg. Allg. Chem.
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Regelmann, B.1
Klinkhammer, K.W.2
Schmidt, A.3
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38
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70349657268
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2S leads to competent reagents for cation-π cyclization; however, 13 is the most easily prepared and crystallized. We propose giving compound 13 the acronym of BDSB for bromodiethylsulfonium bromopentachloroantimonate
-
2S leads to competent reagents for cation-π cyclization; however, 13 is the most easily prepared and crystallized. We propose giving compound 13 the acronym of BDSB for bromodiethylsulfonium bromopentachloroantimonate.
-
-
-
-
39
-
-
70349669716
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2, 1,2dichloroethane, chloroform, and toluene, and insoluble in benzene, hexanes, and pentane. We have observed that 13 is soluble in. acetone, methanol, ethanol, and THF, but reacts with these solvents
-
2, 1,2dichloroethane, chloroform, and toluene, and insoluble in benzene, hexanes, and pentane. We have observed that 13 is soluble in. acetone, methanol, ethanol, and THF, but reacts with these solvents.
-
-
-
-
40
-
-
70349657270
-
-
For the synthesis of these substrates, see the Supporting Information
-
For the synthesis of these substrates, see the Supporting Information.
-
-
-
-
41
-
-
0001432336
-
-
Although not reported to initiate cation-π cyclizations, bis(collidine)halonium triflate and Perchlorate salts have been utilized as sources of electrophilic halogen. For selected examples
-
Although not reported to initiate cation-π cyclizations, bis(collidine)halonium triflate and Perchlorate salts have been utilized as sources of electrophilic halogen. For selected examples, see: a) R. U. Lemieux, A. R. Morgan, Can. J. Chem. 1965, 43, 2190-2197;
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(1965)
Can. J. Chem.
, vol.43
, pp. 2190-2197
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Lemieux, R.U.1
Morgan, A.R.2
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43
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0000657426
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c) Y Tämaru, S. Kawamura, Z. Yoshida, Tetrahedron Lett. 1985, 26, 2885-2888;
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(1985)
Tetrahedron Lett.
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Tämaru, Y.1
Kawamura, S.2
Yoshida, Z.3
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47
-
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70349676330
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2/ AgBF4 and entry 1 for TBCO. Each of these precedents is fully elucidated in the Supporting Information
-
2/ AgBF4 and entry 1 for TBCO. Each of these precedents is fully elucidated in the Supporting Information.
-
-
-
-
48
-
-
70349706356
-
-
3P under the utilized conditions in 71 % yield; we have been, unable to achieve similar results despite several attempts. Rather than, offer any questioning of this precedent, we would argue instead here that our protocol provides for easier execution since temperature control over the course of 30 h is not required
-
3P under the utilized conditions in 71 % yield; we have been, unable to achieve similar results despite several attempts. Rather than, offer any questioning of this precedent, we would argue instead here that our protocol provides for easier execution since temperature control over the course of 30 h is not required.
-
-
-
-
49
-
-
70349664861
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-
' adducts generated
-
' adducts generated.
-
-
-
-
50
-
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70349696973
-
-
In all cases, the stereochemistry of products was confirmed by NMR analysis as well as comparison to published characterization data. In particular, at least in terms of NMR analyses, any alteration in. the axial or equatorial disposition, of groups attached to the carbocycle are highly diagnostic signals. To verify the nerol cyclization case, we obtained a crystal structure for 36 (a picture of which is shown in the Supporting Information) since precedent for cyclizations with these substrates is sparse
-
In all cases, the stereochemistry of products was confirmed by NMR analysis as well as comparison to published characterization data. In particular, at least in terms of NMR analyses, any alteration in. the axial or equatorial disposition, of groups attached to the carbocycle are highly diagnostic signals. To verify the nerol cyclization case, we obtained a crystal structure for 36 (a picture of which is shown in the Supporting Information) since precedent for cyclizations with these substrates is sparse.
-
-
-
-
51
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70349687825
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4 (cf. Ref. [7a])
-
4 (cf. Ref. [7a]).
-
-
-
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52
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70349660373
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3 to the reaction media prior to BDSB addition. It could also be suppressed by adding a cold solution of BDSB very quickly to the substrate
-
3 to the reaction media prior to BDSB addition. It could also be suppressed by adding a cold solution of BDSB very quickly to the substrate.
-
-
-
-
53
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54749122929
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Conceptually, the reagent described herein can be defined as Lewis base activation of a Lewis acid. For a review on this important mode of promoting reactivity from, one of its leading practitioners
-
Conceptually, the reagent described herein can be defined as Lewis base activation of a Lewis acid. For a review on this important mode of promoting reactivity from, one of its leading practitioners, see : S. E. Denmark, G. L. Beutner, Angew. Chem. 2008, 120, 1584-1663;
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(2008)
Angew. Chem.
, vol.120
, pp. 1584-1663
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Denmark, S.E.1
Beutner, G.L.2
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54
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50249134990
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Angew. Chem. Int. Ed. 2008, 47, 1560-1638.
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Angew. Chem. Int. Ed.
, vol.47
, pp. 1560-1638
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-
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55
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69949112440
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For a recent paper on the use of this approach to attempt enantioselective addition of chalcogens such as sulfur onto alkenes
-
For a recent paper on the use of this approach to attempt enantioselective addition of chalcogens such as sulfur onto alkenes, see: S. E. Denmark, W. R. Collins, M. D. Cullin, J. Am. Chem. Soc. 2009, 131, 3490-3492.
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J. Am. Chem. Soc.
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Denmark, S.E.1
Collins, W.R.2
Cullin, M.D.3
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56
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70349679438
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The crystal structure of 1.3 is noted as preliminary since disorder resulting from, halide exchanges between the halogen atoms attached to the antimony counterion prevents a consistent unit cell
-
The crystal structure of 1.3 is noted as preliminary since disorder resulting from, halide exchanges between the halogen atoms attached to the antimony counterion prevents a consistent unit cell.
-
-
-
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57
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0344179193
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G. Allegra, G. E. Wilson, E. Benedetti, C Pedone, R. Albert, J. Am. Chem. Soc. 1970, 92, 4002-4007.
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a) S. A. Snyder, A. L. Zografos, Y Lin, Angew. Chem. 2007, 119, 8334-8339;
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