109946-35-2Relevant academic research and scientific papers
Synthesis of the second generation photoaffinity probes of tautomycin
Sydnes, Magne O.,Isobe, Minoru
, p. 2593 - 2603 (2007/10/03)
Five photoaffinity probes of tautomycin, which possess an aromatic azide with linker attached to the 2-position of tautomycin, were prepared in order to study the binding site of tautomycin with protein phosphatase 1γ. The photoaffinity probes were synthe
A practical semi-synthesis of tautomycin using a hydrolysate of natural tautomycin
Kurono, Masakuni,Isobe, Minoru
, p. 9609 - 9617 (2007/10/03)
A useful and brief semi-synthesis of tautomycin, which can be supplied a large quantity, has been achieved through the coupling reaction of the C21-C26 segment (an epoxide) with the C1-C20 segment (a dithiane), which was derived from the degradation of natural tautomycin, toward the conformational analysis of the C21-C26 moiety and the exploration of structure-activity relationships.
Total synthesis of the serine/threonine-specific protein phosphatase inhibitor tautomycin
Sheppeck II, James E.,Liu, Wen,Chamberlin, A. Richard
, p. 387 - 398 (2007/10/03)
A convergent, asymmetric synthesis of the protein phosphatase inhibitor, tautomycin, is described. The natural product was constructed by joining two major fragments of comparable complexity at the C21-C22 bond. Absolute stereochemistry of the C1-C21 ketone originates from (S)-citronellene and (2R,3S)-geraniol epoxide. The anti stereochemical relationships at C6-C7 and C18-C19 were introduced with Duthaler's chiral titanium propionic enolate. Syn stereochemical relationships at C13-C14 and C23-C24 were established using an Evan's oxazolidinone chiral auxiliary. The spiroketal was efficiently constructed via a one-pot double-alkylation-spirocyclization sequence with acetone N,N-dimethylhydrazone serving as the central linchpin. Final coupling of the two halves using a chelation-controlled Mukaiyama aldol addition followed by deprotection yielded synthetic tautomycin that is identical to the natural product.
Total synthesis of (+)-tautomycin
Tsuboi, Katsunori,Ichikawa, Yoshiyasu,Jiang, Yimin,Naganawa, Atsushi,Isobe, Minoru
, p. 5123 - 5142 (2007/10/03)
The synthesis of Segment B/C corresponding to the C26 through to the C1 positions of tautomycin was achieved by coupling between Segment B (an epoxide) and Segment C (a sulfone carbanion) in the presence of baron trifluoride etherate (BF3·OEt2). Two routes have been developed in esterification of Segment A with Segment BIG. The first route employed Segment A with furan moiety as masked maleic anhydride, In the second route, maleic anhydride as Segment A was directly used to accomplish the improved synthesis. Removal of the silyl protecting group with pyridinium poly(hydrogen fluoride) (HF-Py) at the final step completed the total synthesis of tautomycin.
Synthetic studies on tautomycin synthesis of segment B
Tsuboi, Katsunori,Ichikawa, Yoshiyasu,Naganawa, Atsushi,Isobe, Minoru,Ubukata, Makoto,Isono, Kiyoshi
, p. 5083 - 5102 (2007/10/03)
The synthesis of Segment B corresponding to the C26-C17 portion of tautomycin was accomplished by coupling reaction between the epoxide (Sub-segment B-l) and the dithiane (Subsegment B-2). The degradation product of tautomycin corresponding to the C26-C19 portion was also synthesized from Sub-segment B-1.
Total synthesis of (+)-tautomycin
Shimizu, Satoshi,Nakamura, Sei-Ichi,Nakada, Masahisa,Shibasaki, Masakatsu
, p. 13363 - 13408 (2007/10/03)
A convergent stereocontrolled total synthesis of (+)-tautomycin (1), a specific inhibitor of protein serine/threonine phosphatases, has been achieved through an esterification of the C1.-C7. fragment A'74 with the C1-C26 fragment B'76 by a modified Yamaguchi method and an aldol reaction of the C17-C26 fragment C 5 with the C1-C16 fragment D 6 using LDA as key steps. The fragments 5 and 6 have been constructed in a stereocontrolled manner, respectively.
Total Synthesis of Tautomycin
Oikawa, Masato,Ueno, Tohru,Oikawa, Hideaki,Ichihara, Akitami
, p. 5048 - 5068 (2007/10/02)
A convergent stereocontrolled synthesis of the antifungal antibiotic tautomycin, a potent protein phosphatases inhibitor, has been achieved first via key aldol coupling of two large subunits, a right-hand C1-C21 ketone and a left-hand aldehyde (left from C22).The C1-C10 segment was synthesized through a remote stereochemical control process using a spiroketal template.After joining with the C11-C18 segment, the spiroketal moiety was selectively constructed.Then the right-hand C1-C21 ketone was synthesized via Roush asymmetric crotylboration.The left-hand aldehyde was prepared from a C21-C26 segment and a dialkylmaleic anhydride segment.Completely stereoselective assemblage of the two subunits, the right-hand and the left-hand, was achieved by employing the Mukaiyama aldol reaction.Further functional group manipulation including desilylation, oxidation at C2, and deprotection of tert-butyl ester with concomitant anhydride formation provided tautomycin which was identical with the natural product.As a preliminary study, derivatizations and degradation of the natural product were also examined to support the total synthesis.
Total synthesis of (+)-tautomycin
Ichikawa, Yoshiyasu,Tsuboi, Katsunori,Jiang, Yimin,Naganawa, Atsushi,Isobe, Minoru
, p. 7101 - 7104 (2007/10/02)
Tautomycin molecule was disconnected into 3 retrosynthetic segments, A, B, and C, each of which was synthesized in optically active form. First coupling between Segments B and C was achieved between an epoxide and a sulfone carbanion in the presence of BF
Total synthesis of tautomycin: Efficient aldol coupling of two large subunits
Oikawa, Hideaki,Oikawa, Masato,Ueno, Tohru,Ichihara, Akitami
, p. 4809 - 4812 (2007/10/02)
The total synthesis of tautomycin 1 has been achieved via key aldol condensation of the Left-wing 2 and the Right-wing 3.
