145401-48-5Relevant articles and documents
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.
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.
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.
