Total synthesis of the macrolide (+)-aspicilin by an asymmetrically catalyzed macrocyclization of an ω-Alkynal ester

Wolfgang Oppolzer; Rumen N. Radinov; Jef De Brabander

doi:10.1016/0040-4039(95)00351-C

Total synthesis of the macrolide (+)-aspicilin by an asymmetrically catalyzed macrocyclization of an ω-Alkynal ester

Wolfgang Oppolzer, Rumen N. Radinov, Jef De Brabander

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Abstract

ω-Alkynal ester 3, prepared from (S)-propylene oxide 4, yields the macrocyclic (6R)-allylic alcohol 2 (60% yield, 83% d.e.) in one operation via monohydroboration, boron/zinc-transmetalation and (-)-DAIB "catalyzed" intramolecular alkenylzinc/aldehyde addition. Introduction of the C(2)-C(3) double bond by selenoxide elimination (2 → 8), hydroxy-directed epoxidation (8 → 9), acetate assisted α-epoxide opening (10 → 12) and acidic methanolysis provides pure (+)-aspicilin (1) in 22% overall yield from 4.

Original language	English (US)
Pages (from-to)	2607-2610
Number of pages	4
Journal	Tetrahedron Letters
Volume	36
Issue number	15
DOIs	https://doi.org/10.1016/0040-4039(95)00351-C
State	Published - Apr 10 1995

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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title = "Total synthesis of the macrolide (+)-aspicilin by an asymmetrically catalyzed macrocyclization of an ω-Alkynal ester",

abstract = "ω-Alkynal ester 3, prepared from (S)-propylene oxide 4, yields the macrocyclic (6R)-allylic alcohol 2 (60% yield, 83% d.e.) in one operation via monohydroboration, boron/zinc-transmetalation and (-)-DAIB {"}catalyzed{"} intramolecular alkenylzinc/aldehyde addition. Introduction of the C(2)-C(3) double bond by selenoxide elimination (2 → 8), hydroxy-directed epoxidation (8 → 9), acetate assisted α-epoxide opening (10 → 12) and acidic methanolysis provides pure (+)-aspicilin (1) in 22% overall yield from 4.",

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T1 - Total synthesis of the macrolide (+)-aspicilin by an asymmetrically catalyzed macrocyclization of an ω-Alkynal ester

AU - Oppolzer, Wolfgang

AU - Radinov, Rumen N.

AU - Brabander, Jef De

PY - 1995/4/10

Y1 - 1995/4/10

N2 - ω-Alkynal ester 3, prepared from (S)-propylene oxide 4, yields the macrocyclic (6R)-allylic alcohol 2 (60% yield, 83% d.e.) in one operation via monohydroboration, boron/zinc-transmetalation and (-)-DAIB "catalyzed" intramolecular alkenylzinc/aldehyde addition. Introduction of the C(2)-C(3) double bond by selenoxide elimination (2 → 8), hydroxy-directed epoxidation (8 → 9), acetate assisted α-epoxide opening (10 → 12) and acidic methanolysis provides pure (+)-aspicilin (1) in 22% overall yield from 4.

AB - ω-Alkynal ester 3, prepared from (S)-propylene oxide 4, yields the macrocyclic (6R)-allylic alcohol 2 (60% yield, 83% d.e.) in one operation via monohydroboration, boron/zinc-transmetalation and (-)-DAIB "catalyzed" intramolecular alkenylzinc/aldehyde addition. Introduction of the C(2)-C(3) double bond by selenoxide elimination (2 → 8), hydroxy-directed epoxidation (8 → 9), acetate assisted α-epoxide opening (10 → 12) and acidic methanolysis provides pure (+)-aspicilin (1) in 22% overall yield from 4.

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JO - Tetrahedron Letters

JF - Tetrahedron Letters

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ER -

Total synthesis of the macrolide (+)-aspicilin by an asymmetrically catalyzed macrocyclization of an ω-Alkynal ester

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