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

1984 ◽  
Vol 62 (6) ◽  
pp. 1103-1111 ◽  
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.

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

2019 ◽  
Vol 16 (3) ◽  
pp. 328-341
Author(s):  
Zai-Qun Liu
Keyword(s):  
Total Synthesis ◽  
Nucleophilic Addition ◽  
Vinyl Ketone ◽  
Methyl Vinyl Ketone ◽  
Methyl Vinyl ◽  
Oxidation Reduction ◽  
The Future ◽  
Robinson Annulation

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.

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

1979 ◽  
Vol 57 (11) ◽  
pp. 1397-1398 ◽  
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.

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

1990 ◽  
Vol 68 (1) ◽  
pp. 115-126 ◽  
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.

Copolymerization of methyl vinyl ketone with styrene in the presence of cobalt(II) nitrate

1991 ◽  
Vol 47 (1) ◽  
pp. 329-336 ◽  
Author(s):  
Seizo Masuda ◽  
Keiji Minagawa ◽  
Masami Tanaka ◽  
Yutaka Asahi
Keyword(s):  
Vinyl Ketone ◽  
Methyl Vinyl Ketone ◽  
Methyl Vinyl

Additional conformer observed in the microwave spectrum of methyl vinyl ketone

2011 ◽  
Vol 508 (1-3) ◽  
pp. 10-16 ◽  
Author(s):  
David S. Wilcox ◽  
Amanda J. Shirar ◽  
Owen L. Williams ◽  
Brian C. Dian
Keyword(s):  
Microwave Spectrum ◽  
Vinyl Ketone ◽  
Methyl Vinyl Ketone ◽  
Methyl Vinyl
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