Greg Petruncio, Zachary Shellnutt, Lauren L. Young, Michael Girgis, Wendy K. Strangman, R. Thomas Williamson, Kylene Kehn-Hall and Mikell Paige*,
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引用次数: 0
摘要
每种同种红霉素对映体的合成总共需要 17 个步骤(最长线性序列 = 12 个步骤)和 10 次色谱纯化。我们尝试了多种方案来合成关键的五元环,但只有铃木偶联-分子内弗里德尔-卡夫酰化序列证明是可行的。在天然产物的光学旋转表征过程中遇到的挑战给我们留下了两个重要启示。首先,像同种异红霉素这样在钠 d 线附近/位置吸收的高色度化合物可能需要在其他波长上进行光旋转测量。其次,为了在钠 d 线处进行测量而对此类化合物进行高稀释,可能会导致人为地增大和错误地分配特定旋转。为了验证光学旋转,我们获取了同种异构体的电子圆二色光谱,并通过克拉默-克罗尼格变换将其转换为光学旋转色散。我们注意到旋转与波长有关,在钠 d 线 589 纳米处,我们将 L-高松霉素的光学旋转从 (-) 重新分配为 (+)。
Total Synthesis of Homoseongomycin Enantiomers and Evaluation of Their Optical Rotation
A total synthesis of each homoseongomycin enantiomer was accomplished in 17 total steps (longest linear sequence = 12 steps) and 10 chromatographic purifications. Several schemes were attempted to forge the key 5-membered ring, but only a Suzuki coupling-intramolecular Friedel–Crafts acylation sequence proved viable. Challenges encountered during the optical rotation characterization of the natural product left us with two important takeaways. First, highly colored compounds like homoseongomycin that absorb near/at the sodium d-line may require optical rotation measurements at other wavelengths. Second, high dilution of such compounds to obtain measurement at the sodium d-line could result in artificially large and incorrectly assigned specific rotations. To verify the optical rotation, electronic circular dichroism spectra were acquired for both homoseongomycin enantiomers and were transformed into optical rotary dispersions via the Kramers–Kronig transform. We note the wavelength dependency on rotation, and at the sodium d-line 589 nm, we reassign the optical rotation of L-homoseongomycin from (−) to (+).
ACS OmegaChemical Engineering-General Chemical Engineering
CiteScore
6.60
自引率
4.90%
发文量
3945
审稿时长
2.4 months
期刊介绍:
ACS Omega is an open-access global publication for scientific articles that describe new findings in chemistry and interfacing areas of science, without any perceived evaluation of immediate impact.