Rhenium-Catalyzed Construction of Polycyclic Hydrocarbon Frameworks by a Unique Cyclization of 1,n-Diynes Initiated by 1,1-Difunctionalization with Carbon Nucleophiles

Masahito Murai, Erika Uemura, Shunsuke Hori, Kazuhiko Takai

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

A regioselective cyclization of 1,n-diynes under rhenium catalysis was developed on the basis of a rare type of 1,1-difunctionalization of terminal alkynes with carbon nucleophiles, followed by sequential addition reactions of the resulting alkenylrhenium species. The reaction provides an efficient approach to the synthesis of complex cyclopentane-fused bi- and tricycles and spirocycles, which are useful building blocks for the construction of essential frameworks of biologically active compounds as well as functional materials, from simple starting materials by the formation of up to six new carbon–carbon bonds in a single step. The reaction proceeds under neutral conditions and does not require external ligands or additives. The key to this reactivity is the unique activation mode of the rhenium carbonyl complex, which prefers to interact with heteroatoms in polar carbon–heteroatom bonds as well as nonpolar carbon–carbon unsaturated π bonds.

Original languageEnglish
Pages (from-to)5862-5866
Number of pages5
JournalAngewandte Chemie - International Edition
Volume56
Issue number21
DOIs
Publication statusPublished - May 15 2017

Fingerprint

Cyclic Hydrocarbons
Diynes
Rhenium
Nucleophiles
Cyclization
Carbon
Hydrocarbons
Cyclopentanes
Addition reactions
Bicycles
Functional materials
Alkynes
Catalysis
Chemical activation
Ligands

Keywords

  • 1,1-difunctionalization
  • anti-Markovnikov addition
  • domino reactions
  • metal vinylidenes
  • rhenium

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

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title = "Rhenium-Catalyzed Construction of Polycyclic Hydrocarbon Frameworks by a Unique Cyclization of 1,n-Diynes Initiated by 1,1-Difunctionalization with Carbon Nucleophiles",
abstract = "A regioselective cyclization of 1,n-diynes under rhenium catalysis was developed on the basis of a rare type of 1,1-difunctionalization of terminal alkynes with carbon nucleophiles, followed by sequential addition reactions of the resulting alkenylrhenium species. The reaction provides an efficient approach to the synthesis of complex cyclopentane-fused bi- and tricycles and spirocycles, which are useful building blocks for the construction of essential frameworks of biologically active compounds as well as functional materials, from simple starting materials by the formation of up to six new carbon–carbon bonds in a single step. The reaction proceeds under neutral conditions and does not require external ligands or additives. The key to this reactivity is the unique activation mode of the rhenium carbonyl complex, which prefers to interact with heteroatoms in polar carbon–heteroatom bonds as well as nonpolar carbon–carbon unsaturated π bonds.",
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author = "Masahito Murai and Erika Uemura and Shunsuke Hori and Kazuhiko Takai",
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AU - Murai, Masahito

AU - Uemura, Erika

AU - Hori, Shunsuke

AU - Takai, Kazuhiko

PY - 2017/5/15

Y1 - 2017/5/15

N2 - A regioselective cyclization of 1,n-diynes under rhenium catalysis was developed on the basis of a rare type of 1,1-difunctionalization of terminal alkynes with carbon nucleophiles, followed by sequential addition reactions of the resulting alkenylrhenium species. The reaction provides an efficient approach to the synthesis of complex cyclopentane-fused bi- and tricycles and spirocycles, which are useful building blocks for the construction of essential frameworks of biologically active compounds as well as functional materials, from simple starting materials by the formation of up to six new carbon–carbon bonds in a single step. The reaction proceeds under neutral conditions and does not require external ligands or additives. The key to this reactivity is the unique activation mode of the rhenium carbonyl complex, which prefers to interact with heteroatoms in polar carbon–heteroatom bonds as well as nonpolar carbon–carbon unsaturated π bonds.

AB - A regioselective cyclization of 1,n-diynes under rhenium catalysis was developed on the basis of a rare type of 1,1-difunctionalization of terminal alkynes with carbon nucleophiles, followed by sequential addition reactions of the resulting alkenylrhenium species. The reaction provides an efficient approach to the synthesis of complex cyclopentane-fused bi- and tricycles and spirocycles, which are useful building blocks for the construction of essential frameworks of biologically active compounds as well as functional materials, from simple starting materials by the formation of up to six new carbon–carbon bonds in a single step. The reaction proceeds under neutral conditions and does not require external ligands or additives. The key to this reactivity is the unique activation mode of the rhenium carbonyl complex, which prefers to interact with heteroatoms in polar carbon–heteroatom bonds as well as nonpolar carbon–carbon unsaturated π bonds.

KW - 1,1-difunctionalization

KW - anti-Markovnikov addition

KW - domino reactions

KW - metal vinylidenes

KW - rhenium

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