Question

帮忙翻译一下``谢谢`

Propargylmalonates 1b–e were then tested according to
Equation (4). The generation of a tertiary alkyl radical from
1b is very efficient with dimethyl phosphite (Table 1, entry 1),and the cyclic product 2b is obtained in 91%yield. Substrates
1c and 1d, which bear an ester and a phenyl substituent,
respectively, undergo a radical translocation/cyclization process
to the desired substituted cyclopentanes 2c and 2d in 91
and 55%yield (entries 2 and 3), respectively. Finally, a radical
reaction with substrate 1e gave the cyclopentane derivative in
79% yield[17] (entry 4).
On the basis of these initial results, a method for the rapid
assembly of fused bicyclic compounds was investigated
[Eq. (5)]. Conjugate addition of dimethyl propargylmalonate
to cyclopentenone and cyclohexenone affords the radical
precursors 3a and 3b, respectively. Reaction of 3a and 3b
with dimethyl phosphite and diethyl phosphite proceeds
[Eq. (5)] with complete regioselectivity and affords the fused
bicycles 4a and 4b in 71 and 84% yield as a mixture of two
diastereomers (d.r. 85:15 and 61:39, respectively). Radical
stabilization by the ketone explains the regioselectivity.
Interestingly, the deoxygenated compound 3c gives the
expected bicycloalkanes 4c in 93% yield (d.r. 90:10) under
similar reaction conditions, thus demonstrating that stabilization
of the translocated radical is not a prerequisite for the
formation of fused bicyclic systems [Eq. (6)].
The synthesis of spiro compounds through 1,5-hydrogen
transfer has been reported recently employing an iodoalkenyl
derivative.[18] However, this method suffers from the use of tin
hydride and the difficulty of preparing the starting alkenyl
iodides. On the other hand, substrates 5a–c are readily
prepared by alkylation of the corresponding b-keto ester
followed by decarboxylation and are efficiently converted
[Eq. (7)] into the spiro ketone 6a (97%, d.r. 70:30), 6b (77%,
d.r. 53:47), and 6c (64%, d.r. 79:21).

Answer 1

Propargylmalonates 1b e 然后被测试了根据 等式(4) 。一个三重烷基基础的世代从 1b 是非常高效率的与二甲基亚磷酸盐(表1,词条1), 和循环产品2b 被获得在91%yield 。基体 1.c 和1d, 负担酯类和一个phenyl 代替者, 各自地, 接受一个根本translocation/cyclization 过程 对渴望的被替代的cyclopentanes 2c 和第2 在91 并且55%yield (词条2 和3), 各自地。终于, 基础 反应与基体1e 给了cyclopentane 衍生物 79% yield[17 ] (词条4) 。 根据这些原始结果, 一个方法为迅速 被熔化的两轮并排的化合物汇编被调查了 [ Eq 。(5) ] 。二甲基propargylmalonate 的共轭加法 cyclopentenone 和cyclohexenone 能基础 前体3.a 和3b, 各自地。3.a 和3b 的反应 以二甲基亚磷酸盐和二乙基亚磷酸酯收益 [ Eq 。(5) ] 与完全regioselectivity 和买得起被熔化 自行车4.a 和4b 在71 和84% 出产量作为混合物二 diastereomers (d.r. 85:15 和61:39, 各自地) 。根本 安定由酮解释regioselectivity 。 有趣的是, deoxygenated 复合3c 给 期望的bicycloalkanes 4c 在93% 出产量(d.r. 90:10) 下 相似的反应适应, 如此展示那安定 改变的位置的基础不是一个前提对于 被熔化的两轮并排的系统[ Eq 的形成。(6)] 。 spiro 化合物综合通过1,5 氢 调动被报告了最近使用iodoalkenyl derivative.[18 ] 但是, 这个方法遭受对锡的用途 氢化物和准备开始的链烯基困难 碘化物。另一方面, 基体5.a-c 欣然是 由对应的b keto 酯类的烷化准备 被去碳酸基跟随和高效率地被转换 [ Eq 。(7) ] 入spiro 酮6.a (97%, d.r 。70:30), 6b (77%, d.r. 53:47), 和6c (64%, d.r 。79:21) 。

Answer 2

propargylmalonates1B至电子测试则根据公式(4). 生成烷基自由基从大专1B条很有效率与磷酸二甲酯(表一、 进入1)、2B条生产循环得到91%的产量. 基板1C及1D,承受酯、苯基取代,分别 一个根本性易位/环化进程预期取代cyclopentanes2C及二维和55%产量在91(2条目 3). 最后,激进的反应,与基板1E中作了环戊烷衍生物产量79%[17](进入4). 这些初步成效的基础上,一种为快速融合装配双环化合物被调查[情商. (5)]. 此外轭、环戊烯合成环己烯酮二甲propargylmalonate以使激进前兆3A及3B分别 反应3A及3B与磷酸二甲酯、磷酸二乙酯收益[情商. (五)],并让该区域选择性完全融合自行车4A及4B71、84%产量作为混合物 两名位差(85:15、61:39松驰分别). 激进的镇定酮区域选择性解释. 有趣的无氧化合物116给人的第4C在93%产量预计bicycloalkanes(张力90:10)类似的反应条件下, 显示稳定的前提转急不融合形成双环系统[情商. (6)]. 通过螺化合物合成1,5-氢转移最近有报道利用一套iodoalkenyl衍生. [18]然而, 使用这种方法存在的困难和锡氢化准备出发烯基碘. 在另一方面, 基板5A条-三随时准备相应的烷基乙酮酯、羧其次是转换效率[情商. (7)]进入螺酮52条(97%,张力70:30)第六期(77%、松驰47:53),6C条(64%、松驰79:21).