THE SYNTHESIS OF 4-H-2-ALPHA-FARNESENE AND 1-H-2-ALPHA-FARNESENE

被引:5
作者
FIELDER, S
ROWAN, DD
REAY, PF
机构
[1] Horticulture and Food Research Institute of New Zealand Ltd, Palmerston North, 11030, Private Bag
关键词
ALPHA-FARNESENE; SYNTHESIS; DEUTERIUM LABELING; SULPHOLENE;
D O I
10.1002/jlcr.2580331011
中图分类号
Q5 [生物化学];
学科分类号
071010 ; 081704 ;
摘要
Alpha-Farnesene deuterated at C1 or C4 was synthesised by regiospecific deuteration of 2-geranyl-3-methylsulpholene (2). Treatment of (2) with butyl lithium in dimethylpropenylurea (DMPU) mediated THF resulted in deprotonation at C2. Quenching with D2O/CH3CO2D gave a mixture of deuterated sulpholenes (43-68%), predominantly 2-H-2-2-geranyl-3-methylsulpholene (5), together with bond migrated product (25-49%). Thermal elimination of sulphur dioxide gave 4-H-2-alpha-farnesene (6)(85%) but with low deuterium incorporation (60%) and poor regiospecificity. Treatment of (2) with butyl lithium in TMEDA mediated THF resulted in deprotonation at C5 with minimal bond migration (1%). Quenching with D2O/CH3CO2D yielded 5-H-2-2-geranyl-3-methylsulpholene (18)(75%) which on thermolysis gave 1-H-2-alpha-farnesene (19)(86%) with high regiospecificity and improved deuteration (85%). Some mechanistic aspects of the alkylation of 3-methylsulpholenes are discussed.
引用
收藏
页码:965 / 975
页数:11
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