Total synthesis of mycestericin A and its 14-epimer

Hiroyoshi Yamanaka; Kazuya Sato; Hideyuki Sato; Masatoshi Iida; Takeshi Oishi; Noritaka Chida

doi:10.1016/j.tet.2009.09.012

Total synthesis of mycestericin A and its 14-epimer

Hiroyoshi Yamanaka, Kazuya Sato, Hideyuki Sato, Masatoshi Iida, Takeshi Oishi, Noritaka Chida

School of Medicine

Research output: Contribution to journal › Article › peer-review

29 Citations (Scopus)

Abstract

The total synthesis of mycestericin A (1) and its 14-epimer 34 is described herein. The Overman rearrangement of an allylic trichloroacetimidate derived from l-tartrate generated a tetra-substituted carbon with nitrogen and subsequent stereoselective transformations afforded the highly functionalized left-half segment, vinyl iodide. Cross-coupling of the vinyl iodide with a chiral organometallic species synthesized from d-tartrate under the Negishi or Suzuki-Miyaura coupling conditions, followed by deprotection, completed the total synthesis of 1. The 14-epimer of mycestericin A was also synthesized, and a comparison of [α]_D values of peracetyl γ-lactone derivatives of mycestericin A and its 14-epimer as well as degradation studies of 1 and 34 fully confirmed the proposed absolute structure of mycestericin A.

Original language	English
Pages (from-to)	9188-9201
Number of pages	14
Journal	Tetrahedron
Volume	65
Issue number	45
DOIs	https://doi.org/10.1016/j.tet.2009.09.012
Publication status	Published - 2009 Nov 7

Keywords

Mycestericin A
Negishi coupling
Overman rearrangement
Suzuki-Miyaura coupling
Total synthesis

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tet.2009.09.012

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title = "Total synthesis of mycestericin A and its 14-epimer",

abstract = "The total synthesis of mycestericin A (1) and its 14-epimer 34 is described herein. The Overman rearrangement of an allylic trichloroacetimidate derived from l-tartrate generated a tetra-substituted carbon with nitrogen and subsequent stereoselective transformations afforded the highly functionalized left-half segment, vinyl iodide. Cross-coupling of the vinyl iodide with a chiral organometallic species synthesized from d-tartrate under the Negishi or Suzuki-Miyaura coupling conditions, followed by deprotection, completed the total synthesis of 1. The 14-epimer of mycestericin A was also synthesized, and a comparison of [α]D values of peracetyl γ-lactone derivatives of mycestericin A and its 14-epimer as well as degradation studies of 1 and 34 fully confirmed the proposed absolute structure of mycestericin A.",

keywords = "Mycestericin A, Negishi coupling, Overman rearrangement, Suzuki-Miyaura coupling, Total synthesis",

author = "Hiroyoshi Yamanaka and Kazuya Sato and Hideyuki Sato and Masatoshi Iida and Takeshi Oishi and Noritaka Chida",

note = "Funding Information: This work was supported in part by a Grant-in-Aid for the 21st Century COE Program {\textquoteleft}Keio Life Conjugate Chemistry{\textquoteright} from the Ministry of Education, Culture, Sports, Science, and Technology, Japan.",

year = "2009",

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doi = "10.1016/j.tet.2009.09.012",

language = "English",

volume = "65",

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journal = "Tetrahedron",

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T1 - Total synthesis of mycestericin A and its 14-epimer

AU - Yamanaka, Hiroyoshi

AU - Sato, Kazuya

AU - Sato, Hideyuki

AU - Iida, Masatoshi

AU - Oishi, Takeshi

AU - Chida, Noritaka

N1 - Funding Information: This work was supported in part by a Grant-in-Aid for the 21st Century COE Program ‘Keio Life Conjugate Chemistry’ from the Ministry of Education, Culture, Sports, Science, and Technology, Japan.

PY - 2009/11/7

Y1 - 2009/11/7

N2 - The total synthesis of mycestericin A (1) and its 14-epimer 34 is described herein. The Overman rearrangement of an allylic trichloroacetimidate derived from l-tartrate generated a tetra-substituted carbon with nitrogen and subsequent stereoselective transformations afforded the highly functionalized left-half segment, vinyl iodide. Cross-coupling of the vinyl iodide with a chiral organometallic species synthesized from d-tartrate under the Negishi or Suzuki-Miyaura coupling conditions, followed by deprotection, completed the total synthesis of 1. The 14-epimer of mycestericin A was also synthesized, and a comparison of [α]D values of peracetyl γ-lactone derivatives of mycestericin A and its 14-epimer as well as degradation studies of 1 and 34 fully confirmed the proposed absolute structure of mycestericin A.

AB - The total synthesis of mycestericin A (1) and its 14-epimer 34 is described herein. The Overman rearrangement of an allylic trichloroacetimidate derived from l-tartrate generated a tetra-substituted carbon with nitrogen and subsequent stereoselective transformations afforded the highly functionalized left-half segment, vinyl iodide. Cross-coupling of the vinyl iodide with a chiral organometallic species synthesized from d-tartrate under the Negishi or Suzuki-Miyaura coupling conditions, followed by deprotection, completed the total synthesis of 1. The 14-epimer of mycestericin A was also synthesized, and a comparison of [α]D values of peracetyl γ-lactone derivatives of mycestericin A and its 14-epimer as well as degradation studies of 1 and 34 fully confirmed the proposed absolute structure of mycestericin A.

KW - Mycestericin A

KW - Negishi coupling

KW - Overman rearrangement

KW - Suzuki-Miyaura coupling

KW - Total synthesis

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U2 - 10.1016/j.tet.2009.09.012

DO - 10.1016/j.tet.2009.09.012

M3 - Article

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SN - 0040-4020

VL - 65

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EP - 9201

JO - Tetrahedron

JF - Tetrahedron

IS - 45

ER -

Total synthesis of mycestericin A and its 14-epimer

Abstract

Keywords

ASJC Scopus subject areas

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