STEREOCHEMISTRY OF ADDITION OF ORGANOCOPPER REAGENTS AND OF THE HYDRIDE ION TO 1-(ARYLSULFONYL)BICYCLO[1.1.0]BUTANES
STEREOCHEMISTRY OF ADDITION OF ORGANOCOPPER REAGENTS AND OF THE HYDRIDE ION TO 1-(ARYLSULFONYL)BICYCLO[1.1.0]BUTANES
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DOI：
10.1021/jo00216a027
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发表时间：
1985-01-01
影响因子：
3.6
通讯作者：
POTGIETER, E
中科院分区：
文献类型：
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作者：
GAONI, Y;TOMAZIC, A;POTGIETER, E
在2-外-和2-内甲基-1-(苯磺酰基)双环中添加甲基碘化镁/碘化亚铜或二甲基铜酸锂[1.1.丁烷和测定得到的2，3-二甲基环丁烷中甲基的相对几何构型，使我们能够确定甲基基团的加成来自双环分子的内侧。同样，2-exo，3-和2-endo，3-二甲基二环丁烷的锂铝氢化物还原也被发现是通过双环体系第3位的氢化物离子的内加成而发生的。丁烷(1)可以加成有机铜试剂或用氢化铝锂(LiAlHJ)还原得到环丁烷衍生物2.1，2虽然2的两个几何异构体是通过向未取代的1加成烷基或烯基铜试剂或通过还原其3-甲基衍生物而得到的，3假定1的初级亲核攻击方向是由电子因素和
Addition of methylmagnesium iodide/cuprous iodide or of lithium dimethylcuprate to 2-exo-and 2-endomethyl-1-(phenylsulfonyl) bicyclo [1.1. 0] butane and determination of the relative geometry of the methyls in the 2, 3-dimethylcyclobutanes obtained allowed us to establish that addition of the methyl groupoccurred from the endo side of the bicyclic molecule. Similarly, lithium aluminum hydride reduction of 2-exo, 3-and 2-endo, 3-dimethylbicyclobutane was also found to occur by endo-addition of the hydride ion at position 3 of the bicyclic system.We have recently shown that 1-(phenylsulfonyl) bicycle [1.1. 0] butanes (1) could undergo addition of organocopper reagents or could be reduced with lithium alumi-num hydride (LiAlHJ to provide cyclobutane derivatives 2.1, 2 Although two geometricalisomers of 2 were obtained by addition of alkyl-or alkenylcopper reagents to unsub-situted 1 or by reduction of its 3-methyl derivative, 3 it was assumed that the direction of primary nucleophilic attack on 1 was specifically determined by electronic factors and