How to Start a Total Synthesis from the Wieland-Miescher Ketone?

Background: he Wieland-Miescher ketone consists of a couple of enantiomers of 9-methyl- Δ5(10)-octalin-1,6-dione, in which the configuration at 9-position is S- or R-type. The Robinson annulation of 2-methyl-1,3-cyclohexanedione with methyl vinyl ketone is able to afford the Wieland-Miescher ketone. As widely used in the total synthesis, the Wieland-Miescher ketone is treated at the beginning of total synthesis, and protocols for treating the Wieland-Miescher ketone are worthy to be addressed. Objective: The presented review provides the progress of the usage of Wieland-Miescher ketone for the total synthesis, while treatments on C=C and C=O in the Wieland-Miescher ketone at the beginning of total synthesis are exemplified herein. Conclusion: Modifications of the Wieland-Miescher ketone are composed of oxidation, reduction, and electrophilic or nucleophilic addition. In addition, protection of non-conjugated C=O with glycol or protection of conjugated C=O with ethanedithiol, and the introduction of substituents into α-position of C=C can also be used to modify the structure of the Wieland-Miescher ketone. It is reasonably believed that many novel strategies will be found to treat the Wieland-Miescher ketone in the future total synthesis.

Download Full-text

Total synthesis of steroids. Part 2. Preparation of C-10 methylated steroids. Regio- and stereocontrol in a diene addition to methyl Z-2-methyl-4-oxo-2-pentenoate

Canadian Journal of Chemistry ◽

10.1139/v84-182 ◽

1984 ◽

Vol 62 (6) ◽

pp. 1103-1111 ◽

Cited By ~ 12

Author(s):

Jagabandhu Das ◽

Robert A. Dickinson ◽

Masatoshi Kakushima ◽

Gregory M. Kingston ◽

Gary R. Reid ◽

...

Keyword(s):

Total Synthesis ◽

Vinyl Ketone ◽

Methyl Vinyl Ketone ◽

Twelve Step ◽

Methyl Vinyl ◽

Acetyl Group ◽

Bromine Substitution

A twelve-step total synthesis of 14-epi-androsta-4,9(11),15-triene-3,17-dione from methyl vinyl ketone, 2-methylcyclo-hexane-1,3-dione, acetylene, and methyl Z-2-methyl-4-oxo-2-pentenoate is described. Crucial steps include a stereo- and regio-selective diene addition, an efficient formation of ring D by C-acylation of an acetyl group, and a selective bromine substitution at C-15 in a 15,17-dione intermediate. The stereo- and regioselectivity of the diene addition is generalized for certain other bifunctional aliphatic dienophiles.

Download Full-text

The total synthesis of (±)-15,16-dimethoxyerythrinan-3-one. A further application of the methyl vinyl ketone annelation of endocyclic enamines

Chemical Communications (London) ◽

10.1039/c19680001104 ◽

1968 ◽

Vol 0 (18) ◽

pp. 1104-1105 ◽

Cited By ~ 1

Author(s):

R. V. Stevens ◽

Mark P. Wentland

Keyword(s):

Total Synthesis ◽

Vinyl Ketone ◽

Methyl Vinyl Ketone ◽

Methyl Vinyl

Download Full-text

Total synthesis of 14β-hydroxy-4,9(11)- androstadiene-3,17-dione

Canadian Journal of Chemistry ◽

10.1139/v79-227 ◽

1979 ◽

Vol 57 (11) ◽

pp. 1397-1398 ◽

Cited By ~ 12

Author(s):

Andrzej Robert Daniewski ◽

Peter S. White ◽

Zdenek Valenta

Keyword(s):

Total Synthesis ◽

Title Compound ◽

Aldol Condensation ◽

Vinyl Ketone ◽

Methyl Vinyl Ketone ◽

Chiral Center ◽

Asymmetric Induction ◽

Methyl Vinyl ◽

Chiral Centers

The title compound 8, a potential intermediate in the total synthesis of cardiac-active principles and other polyfunctional steroids, is prepared in nine steps using methyl vinyl ketone and 2-methylcyclohexane-1,3-dione as starting materials and acetylene and 2-methylcyclopentane-1,3-dione as additional sources of carbon atoms. In a crucial aldol condensation leading to the closure of steroid ring C, an efficient asymmetric induction by one chiral center leads to the establishment of three new chiral centers.

Download Full-text

The total synthesis of (+)-ryanodol. Part I. General strategy and search for a convenient diene for the construction of a key tricyclic intermediate

Canadian Journal of Chemistry ◽

10.1139/v90-021 ◽

1990 ◽

Vol 68 (1) ◽

pp. 115-126 ◽

Cited By ~ 28

Author(s):

Pierre Deslongchamps ◽

André Bélanger ◽

Daniel J. F. Berney ◽

Hans-Juerg Borschberg ◽

Robert Brousseau ◽

...

Keyword(s):

Total Synthesis ◽

Alder Reaction ◽

Diels Alder ◽

Vinyl Ketone ◽

Methyl Vinyl Ketone ◽

General Strategy ◽

Methyl Vinyl ◽

Synthetic Strategy ◽

Diels Alder Reaction ◽

Retrosynthetic Analysis

This paper reports a retrosynthetic analysis that led to the conception of a synthetic strategy for the construction of ryanodol (2). The preparation of a key diene, i.e., spirolactone dienone 47 (19 → 31 → 33 → 48 → 49 → 52 → 47), and its Diels–Alder reaction with methyl vinyl ketone are reported. Keywords: strategy, synthesis, ryanodol, diterpene.

Download Full-text