Synthesis of the spermidine alkaloids (-)-(2R,3R)- and (-)-(2R,3S)-3-hydroxycelacinnine:: Macrocyclization with oxirane-ring opening and inversion via cyclic sulfamidates

被引：14

作者：

Khanjin, NA ^{[1
]}

Hesse, M ^{[1
]}

机构：

[1] Univ Zurich, Inst Organ Chem, CH-8057 Zurich, Switzerland

来源：

HELVETICA CHIMICA ACTA | 2003年 / 86卷 / 06期

关键词：

D O I：

10.1002/hlca.200390160

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The two epimers (-)-1a and (-)-1b of the macrocyclic lactam alkaloid 3-hydroxycelacinnine with the (2R,3R) and (2R,3S) absolute configurations, respectively, were synthesized by an alternative route involving macrocyclization with the regio- and stereoselective oxirane-ring opening by the terminal amino group (Schemes 2 and 6). Properly N-protected chiral trans-oxirane precursors provided (2R,3R)-macrocycles after a one-pot deprotection-macrocyclization step under moderate dilution (0.005-0.01m). The best yields (65-85%) were achieved with trifluoroacetyl protection. Macrocyclization of the corresponding cis-oxiranes was unsuccessful for steric reasons. Inversion at OH-C(3) via nucleophilic displacement of the cyclic sulfamidate derivative with NaNO2 led to (2R,3S)-macrocycles. The synthesized (-)-(2R,3S)-3-hydroxycelacinnine ((-)-1b) was identical to the natural alkaloid.

引用

页码：2028 / 2057

页数：30

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