SYNTHESIS OF OPTICALLY-ACTIVE CIS- AND TRANS-1,2-DISUBSTITUTED CYCLOPROPANE DERIVATIVES BY THE SIMMONS-SMITH REACTION OF ALLYL ALCOHOL DERIVATIVES DERIVED FROM (R)-2,3-O-ISOPROPYLIDENEGLYCERALDEHYDE
SYNTHESIS OF OPTICALLY-ACTIVE CIS- AND TRANS-1,2-DISUBSTITUTED CYCLOPROPANE DERIVATIVES BY THE SIMMONS-SMITH REACTION OF ALLYL ALCOHOL DERIVATIVES DERIVED FROM (R)-2,3-O-ISOPROPYLIDENEGLYCERALDEHYDE
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DOI：
10.1021/jo00080a017
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发表时间：
1994-01-14
影响因子：
3.6
通讯作者：
TAGUCHI, T
中科院分区：
文献类型：
--
作者：
MORIKAWA, T;SASAKI, H;TAGUCHI, T
利用(R)-2,3- o -异丙基甘油醛(5)衍生的Z-和e -烯丙醇衍生物6的Simmons-Smith反应合成了具有光学活性的顺式和反式-1,2二取代环丙烷衍生物。6与二乙基锌和二碘甲烷反应生成的环丙烷衍生物7的定量产率为84%，收率为35%至接近100%。在环丙烷化过程中，对Z-6的Ire-asi和E-6的1re-2re具有相同的表面选择性。非对映选择性取决于末端烯丙基氧上的保护基团（R = 6, TBDPS > MOM > Bn）和双键的立体化学（Z >e）。对于TBDPS醚Z-和E-6c，分别得到顺式和反式7c为单一非对映体。结果表明，环丙化反应的立体选择性是由配位试剂的二氧环烯丙基氧（O-1）的定向作用控制的。末端的烯丙基氧（O-2）降低了非对映选择性。该反应用于合成γ -氨基丁酸（GABA） 18、22和ent-22的旋光性环丙烷类似物。
The Simmons-Smith reactions of Z- and E-allyl alcohol derivatives 6 derived from (R)-2,3-O-isopropylideneglyceraldehyde (5) were used for the synthesis of optically active cis- and trans-1,2 disubstituted cyclopropane derivatives. Reaction of 6 with diethyl zinc and diiodomethane gave cyclopropane derivatives 7 in 84% to quantitative yields with 35 to approximate to 100% des. Identical facial selectivities toward the double bonds, Ire-asi for Z-6 and 1re-2re for E-6, were observed in the cyclopropanations. The diastereoselectivity was dependent on the protecting group on the terminal allylic oxygen (R of 6, TBDPS > MOM > Bn) and on the stereochemistry of the double bond (Z > E). For TBDPS ethers Z- and E-6c, cis- and trans-7c were obtained as single diastereomers respectively. It was clearly demonstrated that the stereoselectivity of the cyclopropanation is controlled by the directing effect of the allylic oxygen (O-1) of the dioxolane ring which coordinates to the reagent. The terminal allylic oxygen (O-2) lowered the diastereoselectivity This reaction was applied to the synthesis of optically active cyclopropane analogs of gamma-aminobutyric acid (GABA) 18, 22, and ent-22.