In:
Angewandte Chemie, Wiley, Vol. 132, No. 24 ( 2020-06-08), p. 9844-9853
Abstract:
The development of a concise total synthesis of (±)‐phyllantidine ( 1 ), a member of the securinega family of alkaloids containing an unusual oxazabicyclo[3.3.1]nonane core, is described. The synthesis employs a unique synthetic strategy featuring the ring expansion of a substituted cyclopentanone to a cyclic hydroxamic acid as a key step that allows facile installation of the embedded nitrogen‐oxygen (N−O) bond. The optimization of this sequence to effect the desired regiochemical outcome and its mechanistic underpinnings were assessed both computationally and experimentally. This synthetic approach also features an early‐stage diastereoselective aldol reaction to assemble the substituted cyclopentanone, a mild reduction of an amide intermediate without N−O bond cleavage, and the rapid assembly of the butenolide found in ( 1 ) via use of the Bestmann ylide.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v132.24
DOI:
10.1002/ange.202003829
Language:
English
Publisher:
Wiley
Publication Date:
2020
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