General Method for Preparation of Allenic Zinc Reagents by Three-Carbon Homologation of Triorganozincates: Convergent Three-Component Coupling of Propargylic Substrates, Triorganozincates, and Electrophilic Reagents
General Method for Preparation of Allenic Zinc Reagents by Three-Carbon Homologation of Triorganozincates: Convergent Three-Component Coupling of Propargylic Substrates, Triorganozincates, and Electrophilic Reagents
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通过三有机锌酸盐的三碳同系化制备烯二酸锌试剂的通用方法：炔丙酸底物、三有机锌酸盐和亲电子试剂的收敛三组分偶联
DOI：
10.1021/ja962136w
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发表时间：
1996
影响因子：
15
通讯作者：
A. Oku
中科院分区：
文献类型：
--
作者：
T. Harada;T. Katsuhira;A. Osada;Katsuhiro Iwazaki;Keiji Maejima;A. Oku
以炔丙基为底物（R1 R2 C（X）CH = CH，X = MeSO 2 O，Cl，R2 NCO 2）与三有机锌酸盐（（R3）3 ZnM; R3 =烷基，烯基，芳基，M = Li，MgCl）反应，合成了联烯锌试剂（R1 R2 CCC（R3）ZnL）。用D2 O处理联烯锌试剂得到具有高氘掺入的相应氘代联烯。由此制备的联烯锌试剂与各种亲电试剂（醛、酰氯、I2、NCS和氯硅烷）在γ位进行区域选择性偶联反应，以高产率得到相应的炔丙基衍生物（R1 R2 C（El）C = CR 3，El = RCH（OH），RCO，I，Cl，R3 Si）。含硅联烯锌试剂R1 CHCC（CH_2SiMe_3）ZnL和R1 CHCC（SiPhMe_2）ZnL分别由炔丙基氨基甲酸酯（R1 CH（OCONPh_2）C_2CH）和（TMSCH_2）_3 ZnLi反应和溴代炔丙基甲磺酸酯（R1 CH（OSO_2 Me）C_2CBr）与（PhMe_2Si）_3 ZnLi反应制备。这些试剂与亲电试剂的连续处理提供了更好的结果。
Allenic zinc reagents (R1R2CCC(R3)ZnL) are efficiently prepared by the reaction of propargylic substrates (R1R2C(X)C⋮CH, X = MeSO2O, Cl, R2NCO2) with a variety of triorganozincates ((R3)3ZnM; R3 = alkyl, alkenyl, aryl, M = Li, MgCl). Treatment of the allenic zinc reagents with D2O gives the corresponding deuteroallenes with high deuterium incorporation. The allenic zinc reagents thus prepared undergo a coupling reaction with a variety of electrophiles (aldehydes, acyl chlorides, I2, NCS, and chlorosilanes) regioselectively at the γ position to afford the corresponding propargylic derivatives (R1R2C(El)C⋮CR3, El = RCH(OH), RCO, I, Cl, R3Si) in high yields. Silicon containing allenic zinc reagents R1CHCC(CH2SiMe3)ZnL and R1CHCC(SiPhMe2)ZnL are readily prepared by the reaction of propargylic carbamates (R1CH(OCONPh2)C⋮CH) with (TMSCH2)3ZnLi and by the reaction of bromoproparglic mesylates R1CH(OSO2Me)C⋮CBr with (PhMe2Si)3ZnLi, respectively. Successive treatment of these reagents with electrophiles affords fu...