Reduction Selectivity of 2-Substituted Cyclododecanone and Conformation Analysis of trans-1,2-Disubstituted Cyclododecanes†

doi:10.7503/cjcu20140798

Abstract

Abstract:

To confirm the cis-selectivity on the reduction of 2-substituted cyclododecanone and analyze the preferred conformation of trans-1,2-disubstituted cyclododecanes, the reduction of 2-phenyl/cyclohexylcyclododecanones were carried out at the different reductive reagents and temperatures. Based on these results, a series of trans-1,2-disub- stituted cyclododecanes was prepared via NaBH₄reduction of 2-substituted cyclodode- canones, ring-opening of cyclododecene oxide, Mitsunobu reaction of cis-2-phenyl cyclododecanol and hydrolysis, their preferred conformation were analyzed on the basis of ¹H NMR, ¹³C NMR, X-ray diffraction and quantum chemistry calculation. The results showed that the preferred conformations of trans-1,2-disubstituted cyclododecanes were [3333] square conformation, in which the one group presents at the side-exo position and the other one at the corner-anti. The X-ray diffraction structures of the reductive products of cis-2,12-disubstituted cyclododecanones showed that 1,2,3-trisubstituted cyclodode- canes still take [3333] square conformation, in which the two groups present at the side-exo positions and the hydroxy at the corner-syn, three groups are cis-cis relationships.

Key words: 2-Phenyl/cyclohexylcyclododecanone, trans-1,2-Disubstituted cyclododecane, 1,2,3-Trisubstituted cyclododecane, Conformation analysis

TrendMD:

YANG Mingyan, ZHANG Li, WANG Daoquan, WANG Ming'an. Reduction Selectivity of 2-Substituted Cyclododecanone and Conformation Analysis of trans-1,2-Disubstituted Cyclododecanes^†[J]. Chem. J. Chinese Universities, 2015, 36(3): 489.

Figures/Tables 13

References 42

[1]	Clerici A., Pastori N., Porta O., Eur. J. Org. Chem., 2001, 2001, 2235—2243
[2]	Yadav J. S., Nanda S., Reddy P. T., Rao A. B., J. Org. Chem., 2002, 67, 3900—3903
[3]	Takahiro F., Hideki N., Tsukasa S., EP 1398310,2004-03-17
[4]	Fukuzawa S., Nakano N., Saitoh T., Eur. J. Org. Chem., 2004, 2004, 2863—2867
[5]	Marigo M., Backmann S., Halland N., Braunton A., Jorgensen K. A., Angew. Chem. Int. Ed., 2004, 43, 5507—5510
[6]	Kolodiazhna O. O., Kolodiazhna A. O., Kolodiazhnyi O. I., Tetrahedron: Asymmetry,2013, 24, 37—42
[7]	Wang L. H., Jiang S., Zhang Z. J., Zhang H. Y., Liu Y., Chem. J. Chinese Universities,2013, 34(9), 2108—2113
	(王丽华, 江山, 张志君, 张衡益, 刘育. 高等学校化学学报, 2013, 34(9), 2108—2113)
[8]	Qi F. L., Gao L. X., Han F. S., Chem. Res. Chinese Universities,2014, 30(4), 587—592
[9]	Dong X., Li Y., Gou X. F., Zhao J. L., Hua C. W., Chem. Res. Chinese Universities,2014, 30(3), 383—386
[10]	Ballini R., Palestini C., Tetrahedron Lett., 1994, 35, 5731—5734
[11]	Han X. Y., Wang M. A., Li T. G., Liang X. M., Dong Y. H., Chen F. H., Wang D. Q., Chin. J. Struct. Chem., 2007, 26, 625—631
[12]	Potehkin K. A., Maleev A. V., Struchkov Y. T., Magerramov A. M., Kozmin A. S., Zefirov N. S., Doklady Akademii Nauk,1995, 340, 345—349
[13]	Sharpless K. B., Teranishi A. Y., Bäckvall J. E., J. Am. Chem. Soc., 1977, 99, 3120—3128
[14]	Wolinsky J., Thorstenson J. H., Killinger T. A., J. Org. Chem., 1978, 43, 875—881
[15]	Trost B. M., Ochiai M., MeDougl P. G., J. Am. Chem. Soc., 1978, 100, 7103—7106
[16]	Guindon Y., Young R. N., Frenette R., Syn. Commun., 1981, 11, 391—398
[17]	McMurry J. E., Siemers N. O., Tetrahedron Lett., 1993, 34, 7891—7894
[18]	Becker H., Soler M. A., Sharpless K. B., Tetrahedron,1995, 51, 1345—1376
[19]	Wang Y., Kirsch P., Lebl T., Slawin A. M. Z., O'Hagan D., Beilstein J. Org. Chem., 2012, 8, 1271—1278
[20]	Wang D. Q., Yang X. L., Wang M. A., Liang X. M., You T. B., Acta Chimca Sinica,2002, 60, 475—480
	(王道全, 杨晓亮, 王明安, 梁晓梅, 尤田耙. 化学学报, 2002, 60, 475—480)
[21]	Li T. G., Liu J. P., Han J. T., Fu B., Wang D. Q., Wang M. A., Chin. J. Org. Chem., 2009, 29, 898—903
	(李太公, 刘建平, 韩金涛, 傅斌, 王道全, 王明安. 有机化学, 2009, 29, 898—903)
[22]	Zhang C. Y., Chen S. C., Wang D. Q., Wang M. A., Acta Chimca Sinica,2010, 68, 989—995
	(张春艳, 陈守聪, 王道全, 王明安. 化学学报, 2010, 68, 989—995)
[23]	Zhang C. Y., Chen S. C., Liu J. P., Wang D. Q., Wang M. A., Chin. J. Org. Chem., 2010, 30, 1700—1704
	(张春艳, 陈守聪, 刘吉平, 王道全, 王明安. 有机化学, 2010, 30, 1700—1704)
[24]	Han N., Lei X., Turro N. J., J. Org. Chem., 1991, 56, 2927—2930
[25]	Zhang C. Y., Gong S. Y., Zhang L., Wang D. Q., Wang M. A., Molecules,2010, 15, 699—708
[26]	Chen S. C., Zhang C. Y., Zhang L., Wang D. Q., Wang M. A., Acta Chimca Sinica,2011, 69, 1354—1360
	(陈守聪, 张春艳, 张莉, 王道全, 王明安. 化学学报, 2011, 69, 1354—1360)
[27]	Khorasani S., Fernandes M. A., Perry C. B., Cryst. Growth Des., 2012, 12, 5908—5916
[28]	Yates P. C., Richardson C. M., Theochem., 1996, 363, 17—22
[29]	Kolossvary I., Guida W. C., J. Am. Chem. Soc., 1996, 118, 5011—5019
[30]	Christensen I. T., Jorgensen F. S., J. Comp. Aided Mol. Design., 1997, 11, 385—394
[31]	Pawar D. M., Davis K. L., Brown B. L., Smith S. V., Noe E. A., J. Org. Chem., 1999, 64, 4580—4585
[32]	Dos Santos H. F., Franco M. L., Venancio M. F., Ferreira D. E. C., Anconi C. P. A., Rocha W. R., de Almeida W. B., Int. J. Quantum Chem., 2012, 112, 3188—3197
[33]	Kolochkov V. V., Chernov P. P., Polozov A. M., Antonovskii V. L., Koshel G. N., Antonova T. N., Aganov A. V., Zhurnal Organicheskoi Khimii,1990, 26, 387—392
[34]	Wang M. A., Ma Z. C., Jin S. H, Wang D. Q., Chin. J. Org. Chem., 2002, 22, 594—598
	(王明安, 马祖超, 金淑惠, 王道全. 有机化学, 2002, 22, 594—598)
[35]	Girija C. R., Begum N. S., Karim H. A. M. A., Nagendrappa G., Acta Cryst. E,2004, 60, o1764—o1766
[36]	Terentev A. O., Kutkin A. V., Starikova Z. A., Synthesis,2004, 14, 2356—2366
[37]	Asensio G., Cuenca A., Gavina P., Medio-Simon M., Tetrahedron Lett., 1999, 40, 3939—3940
[38]	Asensio G., Cuenca A., Rodriguez N., Medio-Simon M., Tetrahedron: Asymmetry,2003, 14, 3851—3855
[39]	Brown H. C., Varma V., J. Org. Chem., 1974, 39, 1631—1636
[40]	Brown H. C., Varma V., J. Am. Chem. Soc., 1966, 88, 2871—2871
[41]	Dunitz J. D., Shearer H. M. M., Helv. Chim. Acta,1960, 43, 18—35
[42]	Martine A., Joseph C., Jean-Pierre Z., Bernard W., J. Chim. Phys., 1982, 79, 227—231

Compd.	m.p.(ref.)/℃	Compd.	m.p.(ref.)/℃	Compd.	m.p.(ref.)/℃
1	49—50(49—51^[20,21])	5	118—119(119—120^[22,23])	3a	69—71(69—70^[11,12])
2^*		1a	64—65(64—65^[11,12])	7a	160—161(157—158^[17,18])
3	57—58(58—59^[24])	1b	66—67(66—67^[14])	7b	175—177(170—171^[17,18])
4	110—112(110—111^[20,21])	2a	45—46(44—45^[11,12])

Compd.	m.p.(ref.)/℃	Compd.	m.p.(ref.)/℃	Compd.	m.p.(ref.)/℃
1	49—50(49—51^[20,21])	5	118—119(119—120^[22,23])	3a	69—71(69—70^[11,12])
2^*		1a	64—65(64—65^[11,12])	7a	160—161(157—158^[17,18])
3	57—58(58—59^[24])	1b	66—67(66—67^[14])	7b	175—177(170—171^[17,18])
4	110—112(110—111^[20,21])	2a	45—46(44—45^[11,12])

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.	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