高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (3): 489.doi: 10.7503/cjcu20140798
收稿日期:
2014-09-03
出版日期:
2015-03-10
发布日期:
2015-01-30
作者简介:
联系人简介: 王明安, 男, 博士, 教授, 博士生导师, 主要从事有机合成及新农药创制研究. E-mail: 基金资助:
YANG Mingyan, ZHANG Li, WANG Daoquan, WANG Ming'an*()
Received:
2014-09-03
Online:
2015-03-10
Published:
2015-01-30
Contact:
WANG Ming'an
E-mail:wangma@cau.edu.cn
Supported by:
摘要:
通过研究2-苯基/环己基环十二酮在不同还原剂和温度下的还原反应证实了2-取代环十二酮的还原反应具有cis-选择性. 在此基础上, 通过2-取代环十二酮的NaBH4还原反应、 1,2-环氧环十二烷的开环反应及cis-2-苯基环十二醇的Mitsunobu反应和水解反应制备了一系列trans-1,2-二取代环十二烷; 采用 1H NMR、 13C NMR、 X射线衍射和量子化学计算等方法对其优势构象进行了分析. 结果表明, trans-1,2-二取代环十二烷的优势构象为[3333]方形构象, 1个取代基位于边碳外向位(Side-exo), 另1个位于角碳反向位(Corner-anti). cis-2,12-二取代环十二酮的LiAlH4还原产物的X射线衍射分析结果表明, 生成的1,2,3-三取代环十二烷保持了环十二烷的[3333]方形构象, 2个取代基位于边碳外向位, 羟基位于角碳顺向位(Corner-syn), 取代基呈现出cis-cis关系.
TrendMD:
杨明艳, 张莉, 王道全, 王明安. 2-苯基/环己基环十二酮的还原选择性及trans-1,2-二取代环十二烷的构象分析. 高等学校化学学报, 2015, 36(3): 489.
YANG Mingyan, ZHANG Li, WANG Daoquan, WANG Ming'an. Reduction Selectivity of 2-Substituted Cyclododecanone and Conformation Analysis of trans-1,2-Disubstituted Cyclododecanes†. Chem. J. Chinese Universities, 2015, 36(3): 489.
Compd. | m.p.(ref.)/℃ | Compd. | m.p.(ref.)/℃ | Compd. | m.p.(ref.)/℃ |
---|---|---|---|---|---|
1 | 49—50(49—51[ | 5 | 118—119(119—120[ | 3a | 69—71(69—70[ |
2* | 1a | 64—65(64—65[ | 7a | 160—161(157—158[ | |
3 | 57—58(58—59[ | 1b | 66—67(66—67[ | 7b | 175—177(170—171[ |
4 | 110—112(110—111[ | 2a | 45—46(44—45[ |
Table 1 Melting points of compounds 1—5, 7a and 7b
Compd. | m.p.(ref.)/℃ | Compd. | m.p.(ref.)/℃ | Compd. | m.p.(ref.)/℃ |
---|---|---|---|---|---|
1 | 49—50(49—51[ | 5 | 118—119(119—120[ | 3a | 69—71(69—70[ |
2* | 1a | 64—65(64—65[ | 7a | 160—161(157—158[ | |
3 | 57—58(58—59[ | 1b | 66—67(66—67[ | 7b | 175—177(170—171[ |
4 | 110—112(110—111[ | 2a | 45—46(44—45[ |
Compd. | Appearance | m.p./℃ | Yield(%) | HR-ESI-MS([M+H]+), m/z (cacld.) |
---|---|---|---|---|
6 | White solid | 72—74 | 64 | 265.2525(265.2526) |
8 | Colorless solid | 106—108 | 75 | 349.2531(349.2526) |
9 | White solid | 152—154 | 68 | 421.1810(421.1808) |
2b | White solid | 139—141 | 7 | 257.1115(257.1117) |
3b | Colorless oil | 23 | 231.1786(231.1783) | |
4a | White solid | 103—105 | 31 | 325.1834(325.1837) |
4b | White solid | 132—134 | 2 | 325.1835(325.1837) |
5a | White solid | 108—110 | 70 | 261.2216(261.2218) |
5b | White solid | 73—75 | 56 | 261.2213(261.2218) |
6a/6b | White solid | 91—93 | 86 | 267.2683(267.2688) |
8a | White solid | 98—100 | 75 | 373.2501(373.2502) |
9a | White solid | 118—120 | 80 | 423.1963(423.1964) |
Table 2 Appearance, melting points, yields and HR-ESI-MS data of compounds 2—9
Compd. | Appearance | m.p./℃ | Yield(%) | HR-ESI-MS([M+H]+), m/z (cacld.) |
---|---|---|---|---|
6 | White solid | 72—74 | 64 | 265.2525(265.2526) |
8 | Colorless solid | 106—108 | 75 | 349.2531(349.2526) |
9 | White solid | 152—154 | 68 | 421.1810(421.1808) |
2b | White solid | 139—141 | 7 | 257.1115(257.1117) |
3b | Colorless oil | 23 | 231.1786(231.1783) | |
4a | White solid | 103—105 | 31 | 325.1834(325.1837) |
4b | White solid | 132—134 | 2 | 325.1835(325.1837) |
5a | White solid | 108—110 | 70 | 261.2216(261.2218) |
5b | White solid | 73—75 | 56 | 261.2213(261.2218) |
6a/6b | White solid | 91—93 | 86 | 267.2683(267.2688) |
8a | White solid | 98—100 | 75 | 373.2501(373.2502) |
9a | White solid | 118—120 | 80 | 423.1963(423.1964) |
Compd. | 1H NMR(300 MHz, CDCl3), δ | 13C NMR(75 MHz, CDCl3), δ | |
---|---|---|---|
6 | 2.49—2.44(m, 2H), 2.35—2.32(m, 1H), 1.80—1.51(m, 11H), 1.29—1.13(m, 18H) | 214.68, 58.13, 38.34, 31.97, 29.91, 26.41, 26.29, 26.24, 26.22, 26.19, 25.66, 24.04, 24.00, 23.14, 22.18, 21.89 | |
8 | 7.19—7.14(m, 3H), 7.10—7.05(m, 3H), 7.02—6.98(m, 2H), 6.88—6.84(m, 2H), 4.13(dd, J=11.0, 3.4 Hz, 1H), 2.99—2.96(m, 1H), 2.85(dd, J=13.7, 7.4 Hz, 1H), 2.49(dd, J=13.7, 7.1 Hz, 1H), 2.42—2.38(m, 1H), 1.95—1.90(m, 1H), 1.57—1.23(m, 16H) | 211.57, 140.14, 139.32, 128.74, 128.70, 127.17, 127.99, 126.83, 125.62, 54.62, 51.82, 34.78, 32.46, 28.17, 26.80, 26.60, 24.12, 23.65, 22.75, 22.11, 20.67 | |
9 | 7.56—7.49(m, 3H), 7.35—7.30(m, 2H), 7.23—7.13(m, 3H), 7.03—7.00(m, 2H), 4.39(dd, J=7.6, 3.9 Hz, 1H), 4.14(dd, J=9.9, 3.5 Hz, 1H), 2.31—2.12(m, 3H), 1.72—1.25(m, 15H) | 204.27, 138.59, 137.56, 133.43, 129.23, 128.76, 128.36, 128.11, 127.01, 78.04, 51.61, 36.14, 27.14 26.75, 24.95, 24.47, 24.04, 23.89, 23.68, 22.15 | |
2b | 4.02—3.98(m, 1H), 3.78(q, J=6.5 Hz, 2H), 2.35(brs, 2H), 1.80—1.73(m, 2H), 1.44—1.26(m, 21H) | 170.57, 73.50, 65.46, 40.52, 29.89, 29.68, 24.84, 24.77, 24.13, 23.67, 23.47, 22.11, 21.78, 21.72, 20.13 | |
3b | 3.83(ddd, J=12.5, 4.8, 2.1 Hz, 1H), 2.73(ddd, J=11.5, 4.4, 2.1 Hz, 1H), 2.51(br, 1H), 2.09(s, 3H), 1.86—1.24(m, 20H) | 70.10, 51.25, 29.01, 25.22, 25.15, 25.02, 24.05, 23.91, 23.48, 22.28, 21.89, 21.42, 14.43 | |
4a | 7.94—7.91(m, 2H), 7.70—7.65(m,1H), 7.61—7.56(m, 2H), 4.19—4.12(m,1H), 3.70(d, J=3.7 Hz, 1H, OH), 3.28—3.22(m, 1H), 1.86—1.26(m, 20H) | 138.87, 133.71, 129.13, 128.65, 69.07, 67.12, 32.02, 24.95, 24.44, 24.03, 23.95, 23.66, 23.47, 23.05, 20.66 | |
4b | 7.95—7.91(m, 2H),7.72—7.66(m, 1H),7.63—7.57(m, 2H), 4.13—4.08(m, 1H), 3.29(d, J=3.5 Hz, 1H, OH), 3.18—3.14(m, 1H), 1.96—1.80(m, 20H) | 138.33, 133.93, 129.36, 128.50, 68.66, 64.28(br), 30.29, 25.67, 25.35, 24.41, 23.44, 22.64, 22.44, 21.51, 20.86, 19.05 | |
5a | 7.36—7.31(m, 2H), 7.26—7.21(m, 3H), 4.05—3.99(m, 1H), 2.91—2.84(m, 1H), 1.89—1.80(m, 1H), 1.72—1.67(m, 2H), 1.58—1.23(m, 18H) | 142.14, 129.05, 128.58, 126.72, 72.07, 46.65, 30.52, 29.59, 25.03, 24.76, 23.42, 23.37, 23.12, 22.98, 19.31 | |
5b | 7.35—7.19(m, 5H), 3.85—3.81(m, 1H), 2.93—2.87(m, 1H), 1.92—1.82(m, 2H), 1.79—1.64(m, 1H), 1.53—1.15(m, 18H) | 143.19, 128.64, 128.23, 126.36, 73.47, 46.57, 31.55, 30.15, 24.61, 24.56, 24.08, 23.98, 23.48, 22.12, 21.94, 21.75 | |
Compd. | 1H NMR(300 MHz, CDCl3), δ | 13C NMR(75 MHz, CDCl3), δ | |
6a/6b | 3.76(dd, J=11.0, 6.4 Hz, 1H), 1.73—1.65(m, 6H), 1.57—1.12(m, 27H) | 71.43, 43.96, 37.94, 33.03, 32.38, 29.41, 27.32, 27.06, 26.86, 24.89, 24.73, 24.35, 24.33, 24.28, 23.88, 23.52, 21.31 | |
8a | 7.34—7.12(m, 10H), 3.60—3.56(m,1H), 2.88—2.82(m, 2H), 2.70—2.65(m, 1H), 2.07—1.89(m, 1H), 1.65—1.52(m, 1H), 1.51—1.21(m, 18H) | 142.28, 141.54, 129.18, 128.71, 128.50, 128.09, 126.40, 125.65, 74.38, 47.04, 38.83, 38.24, 27.98, 26.47, 24.42, 23.88, 23.20, 23.06, 22.57, 22.30 | |
9a | 7.96—7.93(m, 2H), 7.70—7.65(m,1H), 7.60—7.55(m, 2H), 7.35—7.29(m, 2H), 7.26—7.22(m,1H), 7.21—7.14(m, 2H), 4.41(d, J=10.5 Hz, 1H), 3.46(d, J=8.4 Hz, 1H), 2.84—2.76(m, 1H), 2.34(br, 1H), 2.14—1.94(m, 2H), 1.65—1.05(m, 16H) | 140.64, 138.23, 133.80, 129.08, 129.01, 128.66, 128.49, 127.01, 72.42, 63.91, 46.65, 27.48, 26.32, 24.53, 23.61, 22.97, 22.85, 22.35, 21.64, 19.28 |
Table 3 1H NMR and 13C NMR data of compounds 2—9
Compd. | 1H NMR(300 MHz, CDCl3), δ | 13C NMR(75 MHz, CDCl3), δ | |
---|---|---|---|
6 | 2.49—2.44(m, 2H), 2.35—2.32(m, 1H), 1.80—1.51(m, 11H), 1.29—1.13(m, 18H) | 214.68, 58.13, 38.34, 31.97, 29.91, 26.41, 26.29, 26.24, 26.22, 26.19, 25.66, 24.04, 24.00, 23.14, 22.18, 21.89 | |
8 | 7.19—7.14(m, 3H), 7.10—7.05(m, 3H), 7.02—6.98(m, 2H), 6.88—6.84(m, 2H), 4.13(dd, J=11.0, 3.4 Hz, 1H), 2.99—2.96(m, 1H), 2.85(dd, J=13.7, 7.4 Hz, 1H), 2.49(dd, J=13.7, 7.1 Hz, 1H), 2.42—2.38(m, 1H), 1.95—1.90(m, 1H), 1.57—1.23(m, 16H) | 211.57, 140.14, 139.32, 128.74, 128.70, 127.17, 127.99, 126.83, 125.62, 54.62, 51.82, 34.78, 32.46, 28.17, 26.80, 26.60, 24.12, 23.65, 22.75, 22.11, 20.67 | |
9 | 7.56—7.49(m, 3H), 7.35—7.30(m, 2H), 7.23—7.13(m, 3H), 7.03—7.00(m, 2H), 4.39(dd, J=7.6, 3.9 Hz, 1H), 4.14(dd, J=9.9, 3.5 Hz, 1H), 2.31—2.12(m, 3H), 1.72—1.25(m, 15H) | 204.27, 138.59, 137.56, 133.43, 129.23, 128.76, 128.36, 128.11, 127.01, 78.04, 51.61, 36.14, 27.14 26.75, 24.95, 24.47, 24.04, 23.89, 23.68, 22.15 | |
2b | 4.02—3.98(m, 1H), 3.78(q, J=6.5 Hz, 2H), 2.35(brs, 2H), 1.80—1.73(m, 2H), 1.44—1.26(m, 21H) | 170.57, 73.50, 65.46, 40.52, 29.89, 29.68, 24.84, 24.77, 24.13, 23.67, 23.47, 22.11, 21.78, 21.72, 20.13 | |
3b | 3.83(ddd, J=12.5, 4.8, 2.1 Hz, 1H), 2.73(ddd, J=11.5, 4.4, 2.1 Hz, 1H), 2.51(br, 1H), 2.09(s, 3H), 1.86—1.24(m, 20H) | 70.10, 51.25, 29.01, 25.22, 25.15, 25.02, 24.05, 23.91, 23.48, 22.28, 21.89, 21.42, 14.43 | |
4a | 7.94—7.91(m, 2H), 7.70—7.65(m,1H), 7.61—7.56(m, 2H), 4.19—4.12(m,1H), 3.70(d, J=3.7 Hz, 1H, OH), 3.28—3.22(m, 1H), 1.86—1.26(m, 20H) | 138.87, 133.71, 129.13, 128.65, 69.07, 67.12, 32.02, 24.95, 24.44, 24.03, 23.95, 23.66, 23.47, 23.05, 20.66 | |
4b | 7.95—7.91(m, 2H),7.72—7.66(m, 1H),7.63—7.57(m, 2H), 4.13—4.08(m, 1H), 3.29(d, J=3.5 Hz, 1H, OH), 3.18—3.14(m, 1H), 1.96—1.80(m, 20H) | 138.33, 133.93, 129.36, 128.50, 68.66, 64.28(br), 30.29, 25.67, 25.35, 24.41, 23.44, 22.64, 22.44, 21.51, 20.86, 19.05 | |
5a | 7.36—7.31(m, 2H), 7.26—7.21(m, 3H), 4.05—3.99(m, 1H), 2.91—2.84(m, 1H), 1.89—1.80(m, 1H), 1.72—1.67(m, 2H), 1.58—1.23(m, 18H) | 142.14, 129.05, 128.58, 126.72, 72.07, 46.65, 30.52, 29.59, 25.03, 24.76, 23.42, 23.37, 23.12, 22.98, 19.31 | |
5b | 7.35—7.19(m, 5H), 3.85—3.81(m, 1H), 2.93—2.87(m, 1H), 1.92—1.82(m, 2H), 1.79—1.64(m, 1H), 1.53—1.15(m, 18H) | 143.19, 128.64, 128.23, 126.36, 73.47, 46.57, 31.55, 30.15, 24.61, 24.56, 24.08, 23.98, 23.48, 22.12, 21.94, 21.75 | |
Compd. | 1H NMR(300 MHz, CDCl3), δ | 13C NMR(75 MHz, CDCl3), δ | |
6a/6b | 3.76(dd, J=11.0, 6.4 Hz, 1H), 1.73—1.65(m, 6H), 1.57—1.12(m, 27H) | 71.43, 43.96, 37.94, 33.03, 32.38, 29.41, 27.32, 27.06, 26.86, 24.89, 24.73, 24.35, 24.33, 24.28, 23.88, 23.52, 21.31 | |
8a | 7.34—7.12(m, 10H), 3.60—3.56(m,1H), 2.88—2.82(m, 2H), 2.70—2.65(m, 1H), 2.07—1.89(m, 1H), 1.65—1.52(m, 1H), 1.51—1.21(m, 18H) | 142.28, 141.54, 129.18, 128.71, 128.50, 128.09, 126.40, 125.65, 74.38, 47.04, 38.83, 38.24, 27.98, 26.47, 24.42, 23.88, 23.20, 23.06, 22.57, 22.30 | |
9a | 7.96—7.93(m, 2H), 7.70—7.65(m,1H), 7.60—7.55(m, 2H), 7.35—7.29(m, 2H), 7.26—7.22(m,1H), 7.21—7.14(m, 2H), 4.41(d, J=10.5 Hz, 1H), 3.46(d, J=8.4 Hz, 1H), 2.84—2.76(m, 1H), 2.34(br, 1H), 2.14—1.94(m, 2H), 1.65—1.05(m, 16H) | 140.64, 138.23, 133.80, 129.08, 129.01, 128.66, 128.49, 127.01, 72.42, 63.91, 46.65, 27.48, 26.32, 24.53, 23.61, 22.97, 22.85, 22.35, 21.64, 19.28 |
Compd. | 5a | 5b | 8a | 9a |
---|---|---|---|---|
Crystal size/mm3 | 0.20×0.15×0.15 | 0.40×0.35×0.10 | 0.55×0.50×0.50 | 0.80×0.40×0.35 |
Empirical formula | C18H28O | C19.5H31.5O | C25H34O | C24H32SO3 |
Formula weight | 260.40 | 281.95 | 350.52 | 400.56 |
Temperature/K | 101.5 | 97.5 | 100.0 | 98.7 |
Crystal system | Monoclinic | Triclinic | Monoclinic | Monoclinic |
Space group | P21/n | P-1 | P21/c | P21/n |
a/nm | 1.51813(8) | 0.93549(19) | 0.55850(4) | 0.56360(5) |
b/nm | 0.59357(7) | 1.3538(2) | 1.44957(6) | 3.18166(18) |
c/nm | 1.6762(4) | 1.3573(3) | 2.48210(12) | 1.15827(9) |
α/(°) | 90.00 | 90.499(15) | 90.00 | 90.00 |
β/(°) | 91.058(12) | 95.688(16) | 93.469(7) | 92.557(9) |
γ/(°) | 90.00 | 91.985(16) | 90.00 | 90.00 |
Volume/nm3 | 1.5102(4) | 1.7093(6) | 2.00577(19) | 2.0749(3) |
Z | 4 | 4 | 4 | 4 |
ρcalc/(mg·mm-3) | 1.145 | 1.096 | 1.161 | 1.282 |
μ/mm-1 | 0.068 | 0.065 | 0.068 | 0.178 |
F(000) | 576 | 626 | 768 | 864 |
2θ range/(°) | 7.18—52 | 5.96—52 | 6.52—52 | 7.04—52 |
Index range | -18 ≤h ≤ 14 | -11 ≤h ≤ 11 | -5 ≤h ≤ 6 | -6 ≤h ≤ 6 |
-3 ≤k ≤ 7 | -16 ≤ k ≤ 16 | -17 ≤k ≤ 11 | -39 ≤k ≤ 21 | |
-19 ≤l ≤ 20 | -16 ≤l ≤ 16 | -30 ≤l ≤ 30 | -13 ≤l ≤ 14 | |
Reflections collected | 5766 | 15423 | 8351 | 8025 |
Independent reflections R(int) | 2969(0.0283) | 6706(0.0346) | 3925(0.0246) | 4059(0.0237) |
Data/restraints/parameters | 2969/0/173 | 6706/6/383 | 3925/0/247 | 4059/0/254 |
GOF | 1.049 | 1.030 | 1.035 | 1.056 |
R1, wR2 [I>2σ(I)] | 0.0530, 0.1045 | 0.0534, 0.1184 | 0.0452, 0.0997 | 0.0406, 0.0826 |
R1, wR2 [all data] | 0.0573, 0.1161 | 0.0694, 0.1276 | 0.0548, 0.1051 | 0.0504, 0.0878 |
Largest diff. peak/hole/(e·nm-3) | 210/-292 | 435/-416 | 226/-243 | 298/-410 |
Completeness | 0.999 | 0.998 | 0.998 | 0.998 |
Table 4 Crystal structure parameters for compounds 5a, 5b, 8a and 9a
Compd. | 5a | 5b | 8a | 9a |
---|---|---|---|---|
Crystal size/mm3 | 0.20×0.15×0.15 | 0.40×0.35×0.10 | 0.55×0.50×0.50 | 0.80×0.40×0.35 |
Empirical formula | C18H28O | C19.5H31.5O | C25H34O | C24H32SO3 |
Formula weight | 260.40 | 281.95 | 350.52 | 400.56 |
Temperature/K | 101.5 | 97.5 | 100.0 | 98.7 |
Crystal system | Monoclinic | Triclinic | Monoclinic | Monoclinic |
Space group | P21/n | P-1 | P21/c | P21/n |
a/nm | 1.51813(8) | 0.93549(19) | 0.55850(4) | 0.56360(5) |
b/nm | 0.59357(7) | 1.3538(2) | 1.44957(6) | 3.18166(18) |
c/nm | 1.6762(4) | 1.3573(3) | 2.48210(12) | 1.15827(9) |
α/(°) | 90.00 | 90.499(15) | 90.00 | 90.00 |
β/(°) | 91.058(12) | 95.688(16) | 93.469(7) | 92.557(9) |
γ/(°) | 90.00 | 91.985(16) | 90.00 | 90.00 |
Volume/nm3 | 1.5102(4) | 1.7093(6) | 2.00577(19) | 2.0749(3) |
Z | 4 | 4 | 4 | 4 |
ρcalc/(mg·mm-3) | 1.145 | 1.096 | 1.161 | 1.282 |
μ/mm-1 | 0.068 | 0.065 | 0.068 | 0.178 |
F(000) | 576 | 626 | 768 | 864 |
2θ range/(°) | 7.18—52 | 5.96—52 | 6.52—52 | 7.04—52 |
Index range | -18 ≤h ≤ 14 | -11 ≤h ≤ 11 | -5 ≤h ≤ 6 | -6 ≤h ≤ 6 |
-3 ≤k ≤ 7 | -16 ≤ k ≤ 16 | -17 ≤k ≤ 11 | -39 ≤k ≤ 21 | |
-19 ≤l ≤ 20 | -16 ≤l ≤ 16 | -30 ≤l ≤ 30 | -13 ≤l ≤ 14 | |
Reflections collected | 5766 | 15423 | 8351 | 8025 |
Independent reflections R(int) | 2969(0.0283) | 6706(0.0346) | 3925(0.0246) | 4059(0.0237) |
Data/restraints/parameters | 2969/0/173 | 6706/6/383 | 3925/0/247 | 4059/0/254 |
GOF | 1.049 | 1.030 | 1.035 | 1.056 |
R1, wR2 [I>2σ(I)] | 0.0530, 0.1045 | 0.0534, 0.1184 | 0.0452, 0.0997 | 0.0406, 0.0826 |
R1, wR2 [all data] | 0.0573, 0.1161 | 0.0694, 0.1276 | 0.0548, 0.1051 | 0.0504, 0.0878 |
Largest diff. peak/hole/(e·nm-3) | 210/-292 | 435/-416 | 226/-243 | 298/-410 |
Completeness | 0.999 | 0.998 | 0.998 | 0.998 |
Entry | Compd. | Reductant | Solvent | T/℃ | t/h | n(cis):n(trans)* |
---|---|---|---|---|---|---|
1 | 5 | NaBH4 | CH3OH | 65 | 16 | 70:30 |
2 | NaBH4 | CH3OH | 25 | 16 | 75:25 | |
3 | NaBH4 | CH3OH | 0 | 16 | 78:22 | |
4 | NaBH4 | CH3OH | -20 | 16 | 86:14 | |
5 | LiAlH4 | THF | 65 | 10 | 72:28 | |
6 | LiAlH4 | THF | 25 | 10 | 78:22 | |
7 | LiAlH4 | THF | 0 | 10 | 79:21 | |
8 | LiAlH4 | THF | -20 | 10 | 82:18 | |
9 | LTTBA | THF | 65 | 8 | 76:24 | |
10 | LTTBA | THF | 25 | 8 | 85:15 | |
11 | LTTBA | THF | 0 | 8 | 86:14 | |
12 | LTTBA | THF | -20 | 8 | 96:4 | |
13 | 6 | NaBH4 | CH3OH | 65 | 120 | 61:39 |
14 | NaBH4 | CH3OH | 25 | 120 | ||
15 | NaBH4 | CH3OH | 0 | 120 | ||
16 | NaBH4 | CH3OH | -20 | 120 | ||
17 | LiAlH4 | THF | 65 | 10 | 51:49 | |
18 | LiAlH4 | THF | 25 | 10 | 58:42 | |
19 | LiAlH4 | THF | 0 | 10 | 61:31 | |
20 | LiAlH4 | THF | -20 | 10 | 64:36 | |
21 | LTTBA | THF | 65 | 24 | 57:43 | |
22 | LTTBA | THF | 25 | 24 | 57:43 | |
23 | LTTBA | THF | 0 | 24 | 61:39 | |
24 | LTTBA | THF | -20 | 24 |
Table 5 Reduction selectivity of compounds 5 and 6
Entry | Compd. | Reductant | Solvent | T/℃ | t/h | n(cis):n(trans)* |
---|---|---|---|---|---|---|
1 | 5 | NaBH4 | CH3OH | 65 | 16 | 70:30 |
2 | NaBH4 | CH3OH | 25 | 16 | 75:25 | |
3 | NaBH4 | CH3OH | 0 | 16 | 78:22 | |
4 | NaBH4 | CH3OH | -20 | 16 | 86:14 | |
5 | LiAlH4 | THF | 65 | 10 | 72:28 | |
6 | LiAlH4 | THF | 25 | 10 | 78:22 | |
7 | LiAlH4 | THF | 0 | 10 | 79:21 | |
8 | LiAlH4 | THF | -20 | 10 | 82:18 | |
9 | LTTBA | THF | 65 | 8 | 76:24 | |
10 | LTTBA | THF | 25 | 8 | 85:15 | |
11 | LTTBA | THF | 0 | 8 | 86:14 | |
12 | LTTBA | THF | -20 | 8 | 96:4 | |
13 | 6 | NaBH4 | CH3OH | 65 | 120 | 61:39 |
14 | NaBH4 | CH3OH | 25 | 120 | ||
15 | NaBH4 | CH3OH | 0 | 120 | ||
16 | NaBH4 | CH3OH | -20 | 120 | ||
17 | LiAlH4 | THF | 65 | 10 | 51:49 | |
18 | LiAlH4 | THF | 25 | 10 | 58:42 | |
19 | LiAlH4 | THF | 0 | 10 | 61:31 | |
20 | LiAlH4 | THF | -20 | 10 | 64:36 | |
21 | LTTBA | THF | 65 | 24 | 57:43 | |
22 | LTTBA | THF | 25 | 24 | 57:43 | |
23 | LTTBA | THF | 0 | 24 | 61:39 | |
24 | LTTBA | THF | -20 | 24 |
Compd. | cis(position of OH) | trans(position of OH) | Compd. | cis(position of OH) | trans(position of OH) | ||||
---|---|---|---|---|---|---|---|---|---|
Side-exo | Corner-syn | Side-exo | Corner-anti | Side-exo | Corner-syn | Side-exo | Corner-anti | ||
1 | 20.84 | 0 | 17.28 | 14.94 | 5 | 11.00 | 0 | 8.99 | 2.26 |
2 | 6.07 | 0 | 7.36 | 7.49 | 6 | 10.58 | 5.98 | 4.31 | 0 |
3 | 20.08 | 2.97 | 1.67 | 0 | 7 | 0 | 0 | 25.27 | 25.27 |
4 | 18.66 | 0 | 23.64 | 11.51 |
Table 6 Relative energy(kJ/mol) of preferred [3333] conformations by quantum mechanics(QM)
Compd. | cis(position of OH) | trans(position of OH) | Compd. | cis(position of OH) | trans(position of OH) | ||||
---|---|---|---|---|---|---|---|---|---|
Side-exo | Corner-syn | Side-exo | Corner-anti | Side-exo | Corner-syn | Side-exo | Corner-anti | ||
1 | 20.84 | 0 | 17.28 | 14.94 | 5 | 11.00 | 0 | 8.99 | 2.26 |
2 | 6.07 | 0 | 7.36 | 7.49 | 6 | 10.58 | 5.98 | 4.31 | 0 |
3 | 20.08 | 2.97 | 1.67 | 0 | 7 | 0 | 0 | 25.27 | 25.27 |
4 | 18.66 | 0 | 23.64 | 11.51 |
Compd. | 1a | 1b | 5a | 5b | [3333][ |
---|---|---|---|---|---|
∠C1—C2—C3—C4/(°) | -165.2(-159.04[ | -163.3 | -158.2(-155.71) | -156.1(-167.96) | -155 |
∠C2—C3—C4—C5/(°) | 70.5(69.73) | 65.4 | 71.7(68.87) | 67.2(62.88) | 67 |
∠C3—C4—C5—C6/(°) | 70.2(69.78) | 67.0 | 70.5(67.43) | 67.7(67.16) | 70 |
∠C4—C5—C6—C7/(°) | -157.0(-161.05) | -160.0 | -160.9(-164.78) | -163.0(-158.64) | -163 |
∠C5—C6—C7—C8/(°) | 66.4(65.07) | 68.9 | 66.9(69.87) | 69.2(68.35) | 70 |
∠C6—C7—C8—C9/(°) | 66.0(68.97) | 68.8 | 66.6(68.71) | 69.5(70.95) | 67 |
∠C7—C8—C9—C10/(°) | -162.1(-158.33) | -160.1 | -158.4(-155.00) | -156.9(-163.02) | -155 |
∠C8—C9—C10—C11/(°) | 69.8(69.16) | 68.2 | 69.5(68.51) | 67.3(69.11) | 68 |
∠C9—C10—C11—C12/(°) | 71.6(69.58) | 67.9 | 70.7(65.83) | 66.6(64.86) | 69 |
∠C10—C11—C12—C1/(°) | -158.1(-161.93) | -159.0 | -162.5(-165.76) | -163.9(-157.46) | -161 |
∠C11—C12—C1—C2/(°) | 66.4(62.04) | 67.8 | 66.0(66.74) | 69.3(69.40) | 69 |
∠C12—C1—C2—C3/(°) | 67.8(72.25) | 74.9 | 65.9(71.45) | 70.6(76.51) | 68 |
Table 7 Torsional angels of some compounds in the crystal structures and [3333] conformations*
Compd. | 1a | 1b | 5a | 5b | [3333][ |
---|---|---|---|---|---|
∠C1—C2—C3—C4/(°) | -165.2(-159.04[ | -163.3 | -158.2(-155.71) | -156.1(-167.96) | -155 |
∠C2—C3—C4—C5/(°) | 70.5(69.73) | 65.4 | 71.7(68.87) | 67.2(62.88) | 67 |
∠C3—C4—C5—C6/(°) | 70.2(69.78) | 67.0 | 70.5(67.43) | 67.7(67.16) | 70 |
∠C4—C5—C6—C7/(°) | -157.0(-161.05) | -160.0 | -160.9(-164.78) | -163.0(-158.64) | -163 |
∠C5—C6—C7—C8/(°) | 66.4(65.07) | 68.9 | 66.9(69.87) | 69.2(68.35) | 70 |
∠C6—C7—C8—C9/(°) | 66.0(68.97) | 68.8 | 66.6(68.71) | 69.5(70.95) | 67 |
∠C7—C8—C9—C10/(°) | -162.1(-158.33) | -160.1 | -158.4(-155.00) | -156.9(-163.02) | -155 |
∠C8—C9—C10—C11/(°) | 69.8(69.16) | 68.2 | 69.5(68.51) | 67.3(69.11) | 68 |
∠C9—C10—C11—C12/(°) | 71.6(69.58) | 67.9 | 70.7(65.83) | 66.6(64.86) | 69 |
∠C10—C11—C12—C1/(°) | -158.1(-161.93) | -159.0 | -162.5(-165.76) | -163.9(-157.46) | -161 |
∠C11—C12—C1—C2/(°) | 66.4(62.04) | 67.8 | 66.0(66.74) | 69.3(69.40) | 69 |
∠C12—C1—C2—C3/(°) | 67.8(72.25) | 74.9 | 65.9(71.45) | 70.6(76.51) | 68 |
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