145401-48-5Relevant academic research and scientific papers
Total synthesis of sphingofungin f by orthoamide-type Overman rearrangement of an unsaturated ester
Tsuzaki, Shun,Usui, Shunme,Oishi, Hiroki,Yasushima, Daichi,Fukuyasu, Takahiro,Oishi, Takeshi,Sato, Takaaki,Chida, Noritaka
, p. 1704 - 1707 (2015)
The total synthesis of sphingofungin F through the Overman rearrangement of an unsaturated ester, which is known to be an unsuitable substrate under standard conditions due to the competitive aza-Michael reaction, is described. The developed conditions enabled the ester to be compatible with the original Overman rearrangement, providing quick access to α,α-disubstituted amino acids by minimizing extra protecting group manipulations and redox reactions.
Total synthesis of sphingofungin F
Li, Min,Wu, Anmei
, p. 2985 - 2988 (2006)
A stereoselective approach toward sphingofungin F has been realized from L-quebrachitol. This synthesis featured a substrate-controlled asymmetric Michael addition, a regiospecific methylsulfonate elimination to construct the contiguous chiral centers in
Synthesis of β-hydroxy-α,α-disubstituted amino acids through the orthoamide-type overman rearrangement of an α,β-unsaturated ester and stereodivergent intramolecular SN2′ reaction: Development and application to the total synthesis of sphingofungin F
Sugai, Tomoya,Usui, Shunme,Tsuzaki, Shun,Oishi, Hiroki,Yasushima, Daichi,Hisada, Shoko,Fukuyasu, Takahiro,Oishi, Takeshi,Sato, Takaaki,Chida, Noritaka
, p. 594 - 607 (2018/04/20)
The development of a two-step synthesis for β-hydroxy-α,α- disubstituted amino acid derivatives from cyclic orthoamide is reported. The first step is the orthoamide-type Overman rearrangement of an α,β-unsaturated ester to give a sterically hindered α,α-disubstituted amidoester. The α,β-unsaturated ester is known to be a challenging substrate in the conventional Overman rearrangement due to the competitive aza-Michael reaction. However, suppression of the aza-Michael reaction is realized by two factors; 1) the high reaction temperature, and 2) an alkyl substituent at the α-position. The second step is stereodivergent intramolecular SN2′ reaction for the installation of a hydroxy group at the β-position. Either syn- or anti-type SN2′ reaction is possible by simply changing the reaction conditions. The developed method can provide all four possible stereoisomers of the β-hydroxy-α,α-disubstituted amino acid, and is successfully applied to the total synthesis of sphingofungin F.
Total Synthesis of Sphingofungin F Based on Chiral Tricyclic Iminolactone
Gan, Feng-Feng,Yang, Shao-Bo,Luo, Yong-Chun,Yang, Wan-Bang,Xu, Peng-Fei
experimental part, p. 2737 - 2740 (2010/07/08)
A new, efficient synthesis of sphingofungin F has been accomplished with 10.4% overall yield in 15 steps. The salient features of the synthesis are the utilization of methyl tricyclic iminolactone 3 for the asymmetric aldol reaction as a key step to intro
Total synthesis of sphingofungin F.
Lee, Kee-Young,Oh, Chang-Young,Ham, Won-Hun
, p. 4403 - 4405 (2007/10/03)
[reaction: see text] A concise, stereocontrolled synthesis of sphingofungin F was achieved. Key features involve diastereoselective oxazoline formation catalyzed by palladium(0), MgBr(2)-promoted gamma-alkoxy allylic stannane addition, and palladium(0)-ca
gem-diacetates as carbonyl surrogates for asymmetric synthesis. Total syntheses of sphingofungins E and F
Trost,Lee
, p. 12191 - 12201 (2007/10/03)
The equivalent of an asymmetric addition to a carbonyl group with a stabilized anion is accomplished by discriminating between the enantiotopic C-O single bonds of a gem-diacetate. In this way, enantioselective total syntheses of two antifugal agents, sph
An efficient and convenient approach to the total synthesis of sphingofungin
Liu,Wang,Lin
, p. 9114 - 9119 (2007/10/03)
As a new member of the sphingofungin family, sphingofungin F exhibits interesting physiological activities with a structural unit of an α-substituted alanine. Described herein is an efficient and convenient stereoselective synthesis of sphingofungin F from L-(+)-tartaric acid, which utilizes Sharpless asymmetric epoxidation of allylic alcohol and Lewis acid-catalyzed intramolecular epoxideopening reaction with an N-nucleophile, to introduce the other two desired stereogenic centers. Side chain functionality was incorporated into the chiral segment using a Wittig reaction.
Catalytic asymmetric syntheses of antifungal sphingofungins and their biological activity as potent inhibitors of serine palmitoyltransferase (SPT)
Kobayashi, Shu
, p. 908 - 919 (2007/10/03)
Unambiguous synthetic routes to sphingofungins B and F and to their stereoisomers have been developed based on the tin(II)-catalyzed asymmetric aldol reaction (Chiral Lewis Acid-Controlled Synthesis (CLAC Synthesis)). Efficient enantioselective synthesis using a catalytic amount of a chiral source as well as the effectiveness of this strategy for the synthesis of the sphingofungin family have been successfully demonstrated. Using the stereoisomers of sphingofungin B synthesized, the relevance of its stereochemistry to its SPT inhibitory activity has been revealed.
Use of heterocycles as chiral ligands and auxiliaries in asymmetric syntheses of sphingosine, sphingofungins B and F
Kobayashi, Shu,Furuta, Takayuki
, p. 10275 - 10294 (2007/10/03)
D-erythro-Sphingosine and its derivatives (dihydrosphingosine, cissphingosine, etc.), sphingofungins B and F have been synthesized from simple achiral compounds using heterocyclic compounds as key chiral ligands and auxiliaries. 5-Benzyloxy-4-ethynyl-2,2-dimethyl-1,3-dioxane (5 or 5- ent), a key intermediate for the synthesis of sphingosine family, was prepared from 1-trimethylsilylpropinal and ketene silyl acetal 4 using a Sn(OTf)2-chiral ligand 1 or 1-ent-catalyzed asymmetric aldol reaction. Sphingosine and its derivatives were readily prepared from 5 according to standard transformation. The chiral hydrophobic side chain (6) of sphingofungin B was synthesized using a catalytic asymmetric aldol reaction using chiral ligand 1-ent. Another key step in the total synthesis of sphingofungin B was a condensation of chiral aldehyde 7 and chiral heterocycle 2. Similarly, the reaction of chiral aldehyde 8 with heterocycle 3 was a key step for the synthesis of sphingofungin F. Highly diastereoselective reactions proceeded smoothly in both cases to afford the corresponding adducts in high yields.
