Total synthesis of (−)-agelastatin A: an SH2′ radical azidation strategy

2018 ◽  
Vol 54 (71) ◽  
pp. 9893-9896 ◽  
Author(s):  
Izuru Tsuchimochi ◽  
Yuta Kitamura ◽  
Hiroshi Aoyama ◽  
Shuji Akai ◽  
Keiyo Nakai ◽  
...  
Keyword(s):  
Total Synthesis ◽  
Synthetic Approach ◽  
Enol Ether ◽  
Agelastatin A ◽  
Silyl Enol Ether ◽  
Strategic Implementation ◽  
Allylic Bromide

A new synthetic approach to (−)-agelastatin A has been established through the strategic implementation of brominative olefin transposition of a silyl enol ether and subsequent SH2′ radical azidation of the resultant allylic bromide.

A New Enantioselective Total Synthesis of Natural Vincamineviaan IntramolecularMannichReaction of an Silyl Enol Ether

1977 ◽  
Vol 60 (5) ◽  
pp. 1801-1810 ◽  
Author(s):  
Wolfgang Oppolzer ◽  
Hartmut Hauth ◽  
Paul Pfäffli ◽  
Roland Wenger
Keyword(s):  
Total Synthesis ◽  
Enol Ether ◽  
Enantioselective Total Synthesis ◽  
Silyl Enol Ether

A total synthesis of a protected form of the secoxyloganin aglucone

1989 ◽  
Vol 67 (2) ◽  
pp. 261-267 ◽  
Author(s):  
Peter T. W. Cheng ◽  
Stewart McLean
Keyword(s):  
Total Synthesis ◽  
Functional Groups ◽  
Oxidation State ◽  
Oxidative Cleavage ◽  
Enol Ether ◽  
Silyl Enol Ether ◽  
Carbon Framework ◽  
High Yields

A synthesis is described that leads from cyclopentadiene through 5-norbornen-2-one to the monosubstituted cyclopentenone 5; a vinyl substituent is attached by the reaction of a cuprate, and the enolate intermediate is trapped as the silyl enol ether 4, which is converted to 19, a product with the 10-carbon framework and stereochemistry of the secoxyloganin aglucone, and with all functional groups differentially protected and in the correct oxidation state. Explorations of the cuprate reaction required to convert the cyclopentenone 5 to the siloxycyclopentene 4 and of the reactions required for the oxidative cleavage of 4 reveal problems with these reactions when they are applied to compounds that are cyclopentane derivatives. The resolution of these problems leads to reaction sequences that proceed with high yields and excellent diastereoselectivity. Keywords: synthesis, secoxyloganin, vinyl cuprate, oxidative cleavage.

Total Synthesis of (±)-Cephalosol via Silyl Enol Ether Acylation

Synthesis ◽  
2010 ◽  
Vol 2010 (06) ◽  
pp. 917-922 ◽  
Author(s):  
Ulrich Koert ◽  
Alexander Arlt
Keyword(s):  
Total Synthesis ◽  
Enol Ether ◽  
Silyl Enol Ether

General Cyclopropane Assembly via Enantioselective Redox-Active Carbene Transfer to Aliphatic Olefins

2018 ◽  
Author(s):  
Marc Montesinos-Magraner ◽  
Matteo Costantini ◽  
Rodrigo Ramirez-Contreras ◽  
Michael E. Muratore ◽  
Magnus J. Johansson ◽  
...  
Keyword(s):  
Total Synthesis ◽  
Asymmetric Synthesis ◽  
Chemical Space ◽  
Synthetic Approach ◽  
Asymmetric Cyclopropanation ◽  
Redox Active ◽  
Wide Range ◽  
Leaving Group ◽  
Stereoelectronic Properties ◽  
Carbene Transfer

Asymmetric cyclopropane synthesis currently requires bespoke strategies, methods, substrates and reagents, even when targeting similar compounds. This limits the speed and chemical space available for discovery campaigns. Here we introduce a practical and versatile diazocompound, and we demonstrate its performance in the first unified asymmetric synthesis of functionalized cyclopropanes. We found that the redox-active leaving group in this reagent enhances the reactivity and selectivity of geminal carbene transfer. This effect enabled the asymmetric cyclopropanation of a wide range of olefins including unactivated aliphatic alkenes, enabling the 3-step total synthesis of (–)-dictyopterene A. This unified synthetic approach delivers high enantioselectivities that are independent of the stereoelectronic properties of the functional groups transferred. Our results demonstrate that orthogonally-differentiated diazocompounds are viable and advantageous equivalents of single-carbon chirons<i>.</i>

Synthesis of α-Arylcarboxylic Acid Amides from Silyl Enol Ether via Migratory Amidation with 2-Azido-1,3-dimethylimidazolinium Hexafluorophosphate

2013 ◽  
Vol 42 (7) ◽  
pp. 691-693 ◽  
Author(s):  
Mitsuru Kitamura ◽  
Kento Murakami ◽  
Yuichiro Shiratake ◽  
Tatsuo Okauchi
Keyword(s):  
Enol Ether ◽  
Silyl Enol Ether

Carbon-carbon bond formation in reactions of PhIO.cntdot.HBF4-silyl enol ether adduct with alkenes or silyl enol ethers

1989 ◽  
Vol 54 (11) ◽  
pp. 2605-2608 ◽  
Author(s):  
V. V. Zhdankin ◽  
M. Mullikin ◽  
Rik Tykwinski ◽  
Bruce Berglund ◽  
Ronald Caple ◽  
...  
Keyword(s):  
Bond Formation ◽  
Enol Ether ◽  
Enol Ethers ◽  
Carbon Bond ◽  
Silyl Enol Ethers ◽  
Carbon Carbon Bond ◽  
Silyl Enol Ether

scholarly journals Total Syntheses of Pladienolide-Derived Spliceosome Modulators

Molecules ◽  
2021 ◽  
Vol 26 (19) ◽  
pp. 5938
Author(s):  
Jaehoon Sim ◽  
Eunbin Jang ◽  
Hyun Jin Kim ◽  
Hongjun Jeon
Keyword(s):  
Total Synthesis ◽  
Natural Product ◽  
Structural Features ◽  
Synthetic Approach ◽  
Synthetic Analog ◽  
Phase I Clinical Trials ◽  
Total Syntheses ◽  
Naturally Occurring ◽  
Anti Cancer ◽  
Synthetic Approaches

Pladienolides, an emerging class of naturally occurring spliceosome modulators, exhibit interesting structural features, such as highly substituted 12-membered macrocycles and epoxide-containing diene side chains. The potential of pladienolides as anti-cancer agents is confirmed by H3B-8800, a synthetic analog of this natural product class, which is currently under Phase I clinical trials. Since its isolation in 2004 and the first total synthesis in 2007, a dozen total syntheses and synthetic approaches toward the pladienolide class have been reported to date. This review focuses on the eight completed total syntheses of naturally occurring pladienolides or their synthetic analogs, in addition to a synthetic approach to the main framework of the natural product.

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