The 2 S configuration of the marine natural product distaminolyne A was recently disputed based upon total synthesis, yet paradoxically supported by a second independent total synthesis from a different research group. We now verify the 2 S configuration of distaminolyne A by extensive chiroptical studies and support the veracity of the EC ECD method originally used to prove it. The origin of the apparent paradox appears to lie in the limits of precision of polarimetry in the context of weakly rotatory molecules, which strikes a cautionary note on the reliability of "reassignment" of natural product configurations based solely on specific rotation.
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An Acetylenic Lipid from the New Zealand Ascidian : Exemplification of an Improved Workflow for Determination of Absolute Configuration of Long-Chain 2-Amino-3-alkanols.
J Nat Prod
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School of Chemical Sciences , University of Auckland, Private Bag 92019, Auckland 1142 , New Zealand.
An acetylenic 2-amino-3-alcohol, distaminolyne B (), isolated from the New Zealand ascidian , is reported. The isolation and structure elucidation of and assignment of 2,3 absolute configuration (AC) using the exciton coupled circular dichroism technique are described. Using a methodologically facile workflow, the same AC was also established by analysis of specific rotation, terminal methyl C-1 δ chemical shift, and NH δ and values of the ,-diacetate derivative.
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J Nat Prod
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School of Chemical Sciences , University of Auckland, Private Bag 92019, Auckland 1142 , New Zealand.
The 2 S configuration of the marine natural product distaminolyne A was recently disputed based upon total synthesis, yet paradoxically supported by a second independent total synthesis from a different research group. We now verify the 2 S configuration of distaminolyne A by extensive chiroptical studies and support the veracity of the EC ECD method originally used to prove it. The origin of the apparent paradox appears to lie in the limits of precision of polarimetry in the context of weakly rotatory molecules, which strikes a cautionary note on the reliability of "reassignment" of natural product configurations based solely on specific rotation.
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Department of Chemistry, University of California, San Diego, 9500 Gilman Drive MC0358, La Jolla, CA 92093, USA.
Sample configurations of distaminolyne A (); isolated from the ascidians and , and collected at different sites in New Zealand, were investigated by two methods: Exciton coupled electronic circular dichroism (EC ECD) of the corresponding ,-dibenzoyl derivative ; and chiral reagent derivatization of with ()- and ()-α-methoxyphenylacetic acid (MPA), followed by ¹H-NMR analysis. Configuration and optical purity of (%ee) was found to vary depending on the geographic distribution of ascidian colonies. An improved method for preparing ,-diarenoyl derivatives of was optimized.
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State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences , No. 555, Zu Chong Zhi Road, Zhangjiang Hi-Tech Park, Shanghai 201203, China.
The first total synthesis of a marine derived polyacetylene, distaminolyne A, and its enantiomer were achieved from the commercially available undec-10-en-1-ol. A key proline-catalyzed asymmetric α-aminooxylation of an aldehyde intermediate was used to introduce the chiral center en route to the enantiomerically pure 1,2-amino alcohols. The absolute configuration of both synthesized enantiomers of distaminolyne A was confirmed by using chiral derivatizing agents, leading to revision of the natural product absolute configuration from 2S to 2R.
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Laboratoire Molécules de Communication et Adaptation des Micro-organismes, UMR 7245 CNRS, Muséum National d'Histoire Naturelle , 57 Rue Cuvier (C.P. 54), 75005 Paris, France.
The first occurrence of an acetylenic 1-amino-2-alcohol, distaminolyne A (1), isolated from the New Zealand ascidian Pseudodistoma opacum, is reported. The isolation and structure elucidation of 1 and assignment of absolute configuration using the exciton coupled circular dichroism technique are described. In addition, a new N-9 hydroxy analogue (2) of the known P.
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