DIASTEREOMERIC MONOCYCLIC DIALLENES - SYNTHESIS AND PROPERTIES OF DIASTEREOMERIC 3,4,9,10-CYCLODODECATETRAENE-1,7-DIONES AND 3,4,10,11-CYCLOTETRADECATETRAENE-1,8-DIONES
DIASTEREOMERIC MONOCYCLIC DIALLENES - SYNTHESIS AND PROPERTIES OF DIASTEREOMERIC 3,4,9,10-CYCLODODECATETRAENE-1,7-DIONES AND 3,4,10,11-CYCLOTETRADECATETRAENE-1,8-DIONES
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DOI：
10.1021/ja00795a021
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发表时间：
1973-01-01
影响因子：
15
通讯作者：
SONDHEIMER, F
中科院分区：
文献类型：
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作者：
GARRATT, PJ;NICOLAOU, KC;SONDHEIMER, F
4，4，9，9-四甲氧基环十二碳-1，6-二烯（3）与溴仿和叔丁醇钾反应，得到6，6，12，12-四溴-3，3，9，9-四甲氧基三环[9.1. 0.05 '7]十二烷（4），主要为反式异构体。用甲基锂在-10 ℃处理4，得到非对映体外消旋（5a）和内消旋（5 b）5，5，11，11-四甲氧基-1，2，7，8-环十二碳四烯的混合物，水解后得到相应的外消旋（6a）和内消旋（6 b）3，4，9，10-环十二碳四烯-1，7-二酮。在（-）-鹰爪豆碱的存在下，使用甲基锂进行5a、5 b的部分不对称合成，得到了光学活性的5a样品，并可以鉴定外消旋和内消旋异构体。二缩酮混合物5a、5 b的组成被证明是相同的，无论是衍生自反式四溴化物还是顺式四溴化物（4a或4 b）作为前体。二缩酮5与甲基锂在35 ° C下重排，得到5，5，11，11-四甲氧基-2，7-三环[7.3. 0.02，7]十二碳二烯（13）。5与钠在液氨中反应得到产物混合物，由此得到m，cw-4，4，10，10-四甲氧基-1，7-环十二碳二烯（21）。21与溴仿和叔丁醇钾反应，得到7，7，14，14-四溴-3，3，10，10-四甲氧基三环[11.1. 0.06’8]十四烷（24），其在-10 ℃下用甲基锂处理，得到非对映体外消旋（25 a）和内消旋（25 b）5，5，12，12-四甲氧基-1，2，8，9-环十四碳四烯的混合物。25 a和25 b水解得到相应的外消旋（26 a）和内消旋（26 b）3，4，10，11-环十四碳四烯-1，8-二酮，这些化合物又通过部分不对称合成鉴定，Skattebpl 2和摩尔和沃德研究了用甲基锂处理相应的二溴环丙烷衍生物制备环烯。3* Skattebpl 2制备了两个单环二联烯，1，2，6，7-环癸四烯（1，n= 2）和1，2，9，10-环己十四烯（1，n = 5），
Reaction of 4, 4, 9, 9-tetramethoxycyclododeca-l, 6-diene (3) with bromoform and potassium tert-butoxide gave 6, 6, 12, 12-tetrabromo-3, 3, 9, 9-tetramethoxytricyclo [9.1. 0.05'7] dodecane (4), predominantly as the anti isomer. Treatment of 4 with methyllithium at—10 gave a mixture of the diastereomeric racemic (5a) and meso (5b) 5, 5, ll, ll-tetramethoxy-l, 2, 7, 8-cyclododecatetraenes, which on hydrolysis gave the corresponding racemic (6a) and meso (6b) 3, 4, 9, 10-cyclododecatetraene-l, 7-diones. A partial asymmetricsynthesis of 5a, 5b using methyllithium in the presence of (—)-sparteine gave an optically active sample of 5a, and allowed the identification of the racemic and meso isomers. The composition of the diketal mixture 5a, 5b was shown to be the same whether derived from the anti or syn tetrabromide (4a or 4b) as a precursor. The diketal 5 rearranged with methyllithium at 35 to give 5, 5, ll, ll-tetramethoxy-2, 7-tricyclo [7.3. 0.02, 7] dodecadiene (13). Reaction of 5 with sodium in liquid ammonia gave a mixture of products, from which m, cw-4, 4, 10, 10-tetramethoxy-l, 7-cyclo-dodecadiene (21) was obtained. Reaction of 21 with bromoform and potassium fert-butoxide gave 7, 7, 14, 14-tetrabromo-3, 3, 10, 10-tetramethoxytricyclo [11.1. 0.06'8] tetradecane (24), which, on treatment with methyllithium at—10, gave a mixture of the diastereomeric racemic (25a) and meso (25b) 5, 5, 12, 12-tetramethoxy-l, 2, 8, 9-cyclotetradecatetraenes. Hydrolysis of 25a and 25b gave the corresponding racemic (26a) and meso (26b) 3, 4, 10, 11-cyclotetradecatetraene-l, 8-diones, these compounds again being identified through a partial asymmetric synthesis.The preparation of cyclic alienes by treatment of the corresponding dibromocyclopropane derivatives with methyllithium has been studied by Skattebpl2 and Moore and Ward. 3* Skattebpl2 prepared two monocyclic diallenes, 1, 2, 6, 7-cyclodecatetraene (1, n= 2) and 1, 2, 9, 10-cyclohexadecatetraene (1,= 5),