Synthesis of arenediynes via the vinylidenecarbene-acetylene rearrangement

Bichismita Sahu; Irishi N.N. Namboothiri; Rachel Persky

doi:10.1016/j.tetlet.2005.02.101

Synthesis of arenediynes via the vinylidenecarbene-acetylene rearrangement

Bichismita Sahu, Irishi N.N. Namboothiri, Rachel Persky

Department of Chemistry

Indian Institute of Technology Bombay

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

13 Scopus citations

Abstract

A convenient method for the two-step synthesis of arenediynes from 1,2-arenedialdehydes is reported. Dibromomethylenation of dialdehydes under Corey-Fuchs conditions (CBr₄, Ph₃P, Zn) provides the tetrabromides in excellent yields. Treatment of the tetrabromides with n-BuLi or LDA affords 3,4-unsaturated 1,5-diynes, the key structural moiety present in several naturally occurring antitumour antibiotics, in varying yields. The key intermediates in these transformations appear to be vinylidenecarbenes or carbenoids, generated in situ via metal-halogen exchange and elimination.

Original language	English
Pages (from-to)	2593-2597
Number of pages	5
Journal	Tetrahedron Letters
Volume	46
Issue number	15
DOIs	https://doi.org/10.1016/j.tetlet.2005.02.101
State	Published - 11 Apr 2005

Bibliographical note

Funding Information:
The authors thank DST, India, for financial assistance and SAIF, IIT Bombay, for NMR data. B.S. thanks CSIR, India, for a scholarship.

Funding

The authors thank DST, India, for financial assistance and SAIF, IIT Bombay, for NMR data. B.S. thanks CSIR, India, for a scholarship.

Funders	Funder number
Department of Science and Technology, Ministry of Science and Technology, India
Council of Scientific and Industrial Research, India
Indian Institute of Technology Bombay

Keywords

Enediynes
Fritsch-Buttenberg-Wiechell rearrangement
Vinylidenecarbene

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10.1016/j.tetlet.2005.02.101

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title = "Synthesis of arenediynes via the vinylidenecarbene-acetylene rearrangement",

abstract = "A convenient method for the two-step synthesis of arenediynes from 1,2-arenedialdehydes is reported. Dibromomethylenation of dialdehydes under Corey-Fuchs conditions (CBr4, Ph3P, Zn) provides the tetrabromides in excellent yields. Treatment of the tetrabromides with n-BuLi or LDA affords 3,4-unsaturated 1,5-diynes, the key structural moiety present in several naturally occurring antitumour antibiotics, in varying yields. The key intermediates in these transformations appear to be vinylidenecarbenes or carbenoids, generated in situ via metal-halogen exchange and elimination.",

keywords = "Enediynes, Fritsch-Buttenberg-Wiechell rearrangement, Vinylidenecarbene",

author = "Bichismita Sahu and Namboothiri, {Irishi N.N.} and Rachel Persky",

note = "Funding Information: The authors thank DST, India, for financial assistance and SAIF, IIT Bombay, for NMR data. B.S. thanks CSIR, India, for a scholarship.",

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AU - Sahu, Bichismita

AU - Namboothiri, Irishi N.N.

AU - Persky, Rachel

N1 - Funding Information: The authors thank DST, India, for financial assistance and SAIF, IIT Bombay, for NMR data. B.S. thanks CSIR, India, for a scholarship.

PY - 2005/4/11

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N2 - A convenient method for the two-step synthesis of arenediynes from 1,2-arenedialdehydes is reported. Dibromomethylenation of dialdehydes under Corey-Fuchs conditions (CBr4, Ph3P, Zn) provides the tetrabromides in excellent yields. Treatment of the tetrabromides with n-BuLi or LDA affords 3,4-unsaturated 1,5-diynes, the key structural moiety present in several naturally occurring antitumour antibiotics, in varying yields. The key intermediates in these transformations appear to be vinylidenecarbenes or carbenoids, generated in situ via metal-halogen exchange and elimination.

AB - A convenient method for the two-step synthesis of arenediynes from 1,2-arenedialdehydes is reported. Dibromomethylenation of dialdehydes under Corey-Fuchs conditions (CBr4, Ph3P, Zn) provides the tetrabromides in excellent yields. Treatment of the tetrabromides with n-BuLi or LDA affords 3,4-unsaturated 1,5-diynes, the key structural moiety present in several naturally occurring antitumour antibiotics, in varying yields. The key intermediates in these transformations appear to be vinylidenecarbenes or carbenoids, generated in situ via metal-halogen exchange and elimination.

KW - Enediynes

KW - Fritsch-Buttenberg-Wiechell rearrangement

KW - Vinylidenecarbene

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Synthesis of arenediynes via the vinylidenecarbene-acetylene rearrangement

Abstract

Bibliographical note

Funding

Keywords

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