Perylenequinone natural products: total syntheses of the diastereomers (+)-phleichrome and (+)-calphostin D by assembly of centrochiral and axial chiral fragments.
Perylenequinone natural products: total syntheses of the diastereomers (+)-phleichrome and (+)-calphostin D by assembly of centrochiral and axial chiral fragments.
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DOI：
10.1021/jo901384h
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发表时间：
2010-01-01
期刊：
影响因子：
--
通讯作者：
Kozlowski MC
中科院分区：
文献类型：
--
作者：
Morgan BJ;Mulrooney CA;O'Brien EM;Kozlowski MC
介绍了（+）-calphostin D的首次全合成和（+）-phleichrome的全合成。收敛合成利用对映体纯的联芳基常见中间体，其通过对映体选择性催化联芳基偶联形成。所建立的轴向手性以良好的保真度转移到苝醌螺旋立体化学。此外，努力集中在立体异构C7，C7′-2-羟丙基基团的安装上。评价了三种建立C7，C7′-立体化学的路线，其中成功的路线涉及与复杂的轴向手性双铜酸酯的双环氧化物烷基化。该策略不仅允许合成calphostin D和phleichrome的非天然异构体用于生物系统的评估，而且还为更复杂的尾孢菌素和竹红菌甲素的合成提供了有价值的信息。
The first total synthesis of (+)-calphostin D and the total synthesis of (+)-phleichrome are outlined. The convergent syntheses utilize an enantiopure biaryl common intermediate, which is formed via an enantioselective catalytic biaryl coupling. The established axial chirality is transferred to the perylenequinone helical stereochemistry with good fidelity. Additionally, efforts focus on the installation of the stereogenic C7,C7′-2-hydroxypropyl groups. Three routes were evaluated to establish the C7,C7′-stereochemistry, in which the successful route involved a double epoxide alkylation with a complex axial chiral biscuprate. This strategy not only allowed the synthesis of the unnatural isomers of calphostin D and phleichrome for assessment in biological systems, but also provided valuable information for the syntheses of the more complex cercosporin and hypocrellin A.
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影响因子：
18.3
作者：
BROWN, HC;RAMACHANDRAN, PV
通讯作者：
RAMACHANDRAN, PV
影响因子：
2.1
作者：
Brimble, MA;Elliott, RJR
通讯作者：
Elliott, RJR
影响因子：
15
作者：
COHEN, T;SCHAMBACH, RA
通讯作者：
SCHAMBACH, RA
影响因子：
1.8
作者：
BROKA, CA
通讯作者：
BROKA, CA
影响因子：
3.6
作者：
BROWN, HC;RANDAD, RS;PERUMAL, PT
通讯作者：
PERUMAL, PT