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CHEMISTRY & BIODIVERSITY – Vol. 6 (2009)
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11, 3J(8ax,7eq)ꢂ J(8ax,9eq)ꢂ J(9ax,8eq)ꢂ J(9ax,10eq)ꢂ3.5, (HaxꢀC(8), HaxꢀC(9)); 1.11 (qd, 2J ¼
3J(7ax,6)¼3J(7ax,8ax)¼12.5, 3J(7ax,8eq)¼3.5, HaxꢀC(7)). 13C-NMR (100.6 MHz, (CD3)2CO): 85.5
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(dd, J(1,P)¼7.4, J(1,F)¼1.8, C(1)); 74.9 (dd, J(5,P)¼7.4, J(5,F)¼1.2, C(5)); 41.6 (d, J(6,P)¼6.2,
C(6)); 33.1 (d, 3J(10,P)¼9.2, C(10)); 25.4 (br. 4J(7,P)ꢂ1, C(7)); 24.9 (C(8)); 24.5 (d, 2J(9,P)¼2.5, C(9)).
31P-NMR (121.5 MHz, (CD3)2CO): ꢀ14.7 (dd, 1J(P,F)¼998, 3J(P,HeqꢀC(5))¼24.8). 19F{1H}-NMR
(282.4 MHz, (CD3)2CO): ꢀ85.4 (d, 1J(F,P)¼998). EI-MS: 194 (<1, Mþ ), 152 (7), 127 (2), 101 (9), 94
(30), 79 (100), 68 (16), 67 (19), 66 (12), 55 (15), 54 (14), 53 (12). CI-MS (NH3): 406 (21, [2MþNH4]þ
212 (100, [MþNH4]þ ), 195 (3, [MþH]þ ).
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(ꢀ)-(1S,3S,6R)-3-Fluoro-2,4-dioxa-3-phosphabicyclo[4.4.0]decane 3-Oxide ((ꢀ)-9a). [a]2D5 ¼ ꢀ13.9
(c¼1.00, acetone). All other data were identical with those of (þ)-9a.
(þ)-(1R,3S,6S)-3-Fluoro-2,4-dioxa-3-phosphabicyclo[4.4.0]decane 3-Oxide ((þ)-9b). Colorless
plates (from Et2O/hexane). M.p. 64–668. Rf (hexane/Et2O 1:3) 0.14. [a]2D5 ¼ þ35.6 (c¼1.00, acetone).
IR (CHCl3): 3008w, 2945m, 2866m, 1604w, 1475w, 1451w, 1388w, 1327s, 1310s, 1158w, 1139w, 1095m,
1069s, 1055m, 1040s, 1007m, 962m, 900m, 883m, 868m, 854m, 836w, 635w. 1H-NMR (400 MHz,
(CD3)2CO): 4.47 (A of ABX-P, J ¼ 3J(5eq,P)¼10.7, J(5eq,6)¼5.2, HeqꢀC(5))10); 4.46 (m, w1/2 ꢂ25,
HꢀC(1)); 4.28 (B of ABX-P, 2J ¼ 3J(5ax,6)¼3J(5ax,P)¼10.7, 4J(5ax,F)¼1.7, HaxꢀC(5))10); 2.19 (m,
w1/2 ꢂ25, X of ABX-P, HꢀC(6)); 2.13 (m, br. d-like, w1/2 ꢂ20, 2Jꢂ12, HeqꢀC(10)); 1.87–1.78 (m,
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HeqꢀC(7), HeqꢀC(9)); 1.74 (m, br. d-like, w1/2 ꢂ18, Jꢂ12, HeqꢀC(8)); 1.52 (br. qd, Jꢂ J(10ax,1)ꢂ
3J(10ax,9ax)ꢂ12, J(10ax,9eq)¼3.7, HaxꢀC(10)); 1.37 (sext.t-like, Jꢂ12.5, J(8ax,7ax)ꢂ J(8ax,9ax)ꢂ
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3J(9ax,10ax)ꢂ11, 3J(8ax,7eq)ꢂ J(8ax,9eq)ꢂ J(9ax,8eq)ꢂ J(9ax,10eq)ꢂ3.5, (HaxꢀC(8), HaxꢀC(9));
(1.12 (qd, 2J¼3J(7ax,6)¼3J(7ax,8ax)¼12.5, 3J (7ax,8eq)¼3.5, HaxꢀC(7)). 13C-NMR (100.6 MHz,
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(CD3)2CO): 85.1 (d, J(1,P)¼5.8, C(1)); 74.7 (d, J(5,P)¼7.1, C(5)); 40.3 (d, J(6,P)¼13.2, C(6)); 33.4
(d, J(10,P)¼5.9, C(10)); 26.4 (C(7)); 24.7 (C(8)); 24.3 (C(9)). 31P-NMR (121.5 MHz, (CD3)2CO): ꢀ
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14.6 (dt, 1J(P,F)¼983, 3J(P,HaxꢀC(5)¼3J(P,HeqꢀC(5)¼10.7))10). 19F{1H}-NMR (282.4 MHz,
(CD3)2CO): ꢀ67.3 (d, 1J(F,P)¼983). EI-MS: 194 (1, Mþ ), 152 (15), 139 (4), 127 (2), 101 (18), 94
(47), 79 (100), 68 (24), 67 (28), 66 (18), 55 (21), 54 (20), 53 (17). CI-MS (NH3): 406 (21, [2MþNH4]þ
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212 (100, [MþNH4]þ ), 195 (3, [MþH]þ ). CI-MS (NH3): 406 (9, [2MþNH4]þ ) 212 (100, [MþNH4]þ ),
195 (2, [MþH]þ ).
(ꢀ)-(1S,3R,6R)-3-Fluoro-2,4-dioxa-3-phosphabicyclo[4.4.0]decane 3-Oxide ((ꢀ)-9b). [a]2D5 ¼ ꢀ35.3
(c¼1.00, acetone). All other data were identical with those of (þ)-9b.
(þ)-(1S,3S,6S)-3-Fluoro-2,4-dioxa-3-phosphabicyclo[4.4.0]decane 3-Oxide ((þ)-10a). Slightly yel-
lowish viscous oil. Rf (hexane/Et2O 1:3) 0.15. [a]2D5 ¼ þ18.2 (c¼1.00, acetone). IR (CHCl3): 3030w,
2945m, 2871w, 1474w, 1450m, 1434w, 1371w, 1325s, 1157w, 1113m, 1092s, 1067s, 1014s, 987s, 959m, 916m,
899s, 874m, 846m, 826m, 621w. 1H-NMR (400 MHz, (CD3)2CO): 4.98 (q-like, 3J(1,6)ꢂ J(1,10ax)ꢂ
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3J(1,10eq)ꢂ2, HꢀC(1)); 4.63 (A of ABX-P, 2J¼11.4, 3J(5ax,P)¼2.7, 3J(5ax,6)ꢂ0, HaxꢀC(5))11); 4.30 (B
of ABX-P, 2J¼11.4, 3J(5eq,P)¼25.3, 3J(5eq,6)¼1.3, HeqꢀC(5))10); 2.02 (br. d-like, w1/2 ꢂ18, 2Jꢂ13,
HeqꢀC(10)); 1.97 (m, w1/2 ꢂ25, X of ABX-P, HꢀC(6)); 1.81 (m, dt-like, w1/2 ꢂ25, HeqꢀC(7));
HeqꢀC(8)); 1.74–1.63 (m, HaxꢀC(8), HaxꢀC(10)); 1.58–1.49 (m, tt-like, CH2(9)); 1.41 (qd-like, w1/2
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25, HaxꢀC(7)). 13C-NMR (100.6 MHz, (CD3)2CO): 82.0 (dd, J(1,P)¼7.1, J(1,F)¼1.8, C(1)); 75.8 (dd,
2J(5,P)¼7.12, 3J(5,F)¼1.2, C(1), C(5)); 36.5 (d, 3J(6,P)¼5.3, C(6)); 31.8 (d, 3J(10,P)¼9.2, C(10)); 25.2
(C(7)); 23.6 (C(8)); 19.7 (C(9)). 31P-NMR (121.5 MHz, (CD3)2CO): ꢀ14.9 (dddd, 1J(P,F)¼996,
3J(P,HeqꢀC(5)¼25.3, 3J(P,HaxꢀC(5))¼2.7, 4J(P,HaxꢀC(10))¼7.3 ))11). 19F{1H}-NMR (282.4 MHz,
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(CD3)2CO): ꢀ85.2 (d, J(F,P)¼996). EI-MS: 194 (<1, Mþ ), 152 (9), 139 (2), 127 (1), 101 (13), 94
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(45), 79 (100), 68 (19), 67 (23), 66 (14), 55 (16), 54 (17), 53 (13). CI-MS (NH3): 406 (100, [2MþNH4]þ
212 (97, [MþNH4]þ ), 389 (16, [2MþH]þ ) 195 (2, [MþH]þ ).
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The descriptors ꢂaxꢃ and ꢂeqꢃ for the H-atoms CH2(5) are based on their relative positions in the
chair conformation of the 2,4-dioxa-3-phospha moiety. Due to the anomeric effect, the heterocycle
is rather a twist-boat than a chair in the P(3)-equatorially-substituted compounds. For reasons of
simplicity, the notation ꢂaxꢃ and ꢂeqꢃ has been maintained; HaxꢀC(5) is always cis to HꢀC(1), and
HeqꢀC(5) trans to HꢀC(1).
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Unambiguously assigned by H{31P} and 31P/1H-correlated spectra (HMQC).
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