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Synlett 2005(20): 3099-3102  
DOI: 10.1055/s-2005-921934
LETTER
© Georg Thieme Verlag Stuttgart · New York

Microwave-Assisted Rearrangement of Vinylaziridines to 3-Pyrrolines: Formal Synthesis of (-)-Anisomycin

Sebastian Hirner, Peter Somfai*
KTH Chemical Science and Engineering, Organic Chemistry, 100 44 Stockholm, Sweden
Fax: +46(8)7912333; e-Mail: somfai@kth.se;
Further Information

Publication History

Received 14 October 2005
Publication Date:
28 November 2005 (online)

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Abstract

An efficient microwave-assisted rearrangement of activated vinylaziridines to 3-pyrrolines is described. The rearrangement proceeds in good to excellent yields and is mediated by NaI or LiI in MeCN at elevated temperatures. The synthetic utility of this reaction is shown in an efficient formal total synthesis of the antibiotic (-)-anisomycin.

Key words

vinylaziridines - pyrrolines - rearrangement - ring expansion - total synthesis

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5

Vinylaziridines 1a,b were synthesized from the corresponding vinylepoxides. [10b]

6

The cis- and trans-vinylaziridines can be distinguished by the 3 J HH coupling constant of the ring protons (cis ca. 6.8-8.4 Hz; trans ca. 4.1-4.4 Hz).

17

For ee determination, the chlorohydrine was converted to the corresponding vinylepoxide by treatment with 5 equiv DBU in CH2Cl2 (r.t., 12 h, 96%). [16b] The ee was shown to be >95% by chiral HPLC analysis (Chiracel OD, hexane-i-PrOH, 99.5:0.5, 0.5 mL/min).

18

[α]D 25 -99.9 (c 1.20, THF) {lit: [α]D 25 -93.8 (c 0.485, THF); [15c] [α]D 25 -101.2 (c 1.44, THF); [15d] [α]D 25 -89.3 (c 1.26, THF) [15e] }.

19

[α]D 25 -48.4 (c 0.37, CH2Cl2).