SYNTHESIS AND ACTIVITY OF OPTICALLY-ACTIVE DISPARLURE
SYNTHESIS AND ACTIVITY OF OPTICALLY-ACTIVE DISPARLURE
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DOI：
10.1021/ja00832a055
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发表时间：
1974-01-01
影响因子：
15
通讯作者：
MARUMO, S
中科院分区：
文献类型：
--
作者：
IWAKI, S;MARUMO, S
HC1)，在1 N hcl -乙酸-水（2:3:4）中用亚硝酸脱氨，得到(6)2（80%）内酯酸。随着脱胺反应的进行，构型保留在手性中心，36应该具有S构型（6的甲酯，[a] 12D+ 14.6 (c 1.7, MeOH)）。6在苯中与草酰氯转化为氯酸(7)，氯酸与二癸基镉缩合生成内酯酮(8)（6的总收率为34%）。用NaBHq在甲醇中还原8，得到内酯醇（9和10）的非对映二聚体混合物（81%）。每一种非对映体都是通过预处理tic（硅胶，乙酸乙酯-/·/-己烷）和重复重结晶（乙酸乙酯-石油醚）分离得到完全纯净的。9通过以下性质被鉴定为45 '，5S构型的5-羟基戊烷-4-olide: mp 66.0；[a] 20D+ 29.2 {c 1.2, CHC13)；质量m/e 256 (m +)；nmr (CDC13) 5 4.46 (1 H, m), 3.60 (1 H, bm), 2.92 (bs， OH), 2.58 (2 H, m), 2.24 (2 H, m), 0.89 （3 H，一个几乎耦合的三重态）。数据10 (mp 63.5;[a] 20D+ 14.8 (c 1.2, CHCI3)；质量m/e 256 (m +)；4.48 (1 H, in), 3.96 (1 H, bm), 2.60 （2 H, m，和1）
HC1), was deaminated with nitrous acid in 1 N HCl-acetic acid-water (2: 3: 4) to give a lactone acid (6) 2 (80%). As the deamination reaction proceeds with retention of configuration at the chiral center, 3 6 should have the S configuration (the methyl ester of 6,[a] 12D+ 14.6 (c 1.7, MeOH)). 6 was converted with oxalyl chloride in benzene to the acid chloride (7), which was condensed with didecylcadmium to yield a lactone ketone (8)(34% overall yield from 6). Re-duction of 8 with NaBHq in methanol afforded a diastereo-meric mixture of a lactone alcohol (9 and10)(81%). Each diastereomer was isolated in a completely purestate by pre-parative tic (silica gel, ethyl acetate-/·/-hexane) followed by repeated recrystallization (ethyl acetate-petroleum ether). 9 was identified as 5-hydroxypentadecan-4-olide with a 45", 5S configuration4 by the following properties: mp 66.0;[a] 20D+ 29.2 {c 1.2, CHC13); mass m/e 256 (M+); nmr (CDC13) 5 4.46 (1 H, m), 3.60 (1 H, bm), 2.92 (bs, OH), 2.58 (2 H, m), 2.24 (2 H, m), 0.89 (3 H, a virtually coupling triplet). Data for 10 (mp 63.5;[a] 20D+ 14.8 (c 1.2, CHCI3); mass m/e 256 (M+); 4.48 (1 H, in), 3.96 (1 H, bm), 2.60 (2 H, m, and 1