Electrophilic aromatic prenylation via cascade cyclization

John G. Kodet; Joseph J. Topczewski; Kevyn D. Gardner; David F. Wiemer

doi:10.1016/j.tet.2013.08.056

Electrophilic aromatic prenylation via cascade cyclization

John G. Kodet, Joseph J. Topczewski, Kevyn D. Gardner, David F. Wiemer

Chemistry (Twin Cities)

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

2 Scopus citations

Abstract

To gain access to prenylated hexahydroxanthenes, tandem cascade cyclization-electrophilic aromatic substitution reactions have been studied on substrates bearing allylic and propargylic substituents. Both BF ₃·OEt₂ and TMSOTf can be used to initiate this reaction sequence, resulting in different ratios of the C-2 and C-6 substitution products. Even though allylic transposition is observed in some cases, the results of a crossover experiment are consistent with an intramolecular reaction sequence. Taken together, these studies now allow preparation of either the C-2 or C-6 prenylated hexahydroxanthene products.

Original language	English (US)
Pages (from-to)	9212-9218
Number of pages	7
Journal	Tetrahedron
Volume	69
Issue number	44
DOIs	https://doi.org/10.1016/j.tet.2013.08.056
State	Published - Nov 4 2013

Bibliographical note

Funding Information:
Financial support from the ACS Division of Medicinal Chemistry (in the form of a predoctoral fellowship to J.J.T.), the University of Iowa Graduate College (in the form of a Presidential Fellowship to J.G.K.), the Roy J. Carver Charitable Trust , and the National Cancer Institute ( R41CA126020 via Terpenoid Therapeutics, Inc.) is gratefully acknowledged.

Keywords

Cationic
Cyclization
Electrophilic aromatic substitution
Prenylation
Tandem reactions

Access

10.1016/j.tet.2013.08.056

OpenUrl availability

Full text

Cite this

@article{28ff1370cc194c61b380ce6bed1f9bf2,

title = "Electrophilic aromatic prenylation via cascade cyclization",

abstract = "To gain access to prenylated hexahydroxanthenes, tandem cascade cyclization-electrophilic aromatic substitution reactions have been studied on substrates bearing allylic and propargylic substituents. Both BF 3·OEt2 and TMSOTf can be used to initiate this reaction sequence, resulting in different ratios of the C-2 and C-6 substitution products. Even though allylic transposition is observed in some cases, the results of a crossover experiment are consistent with an intramolecular reaction sequence. Taken together, these studies now allow preparation of either the C-2 or C-6 prenylated hexahydroxanthene products.",

keywords = "Cationic, Cyclization, Electrophilic aromatic substitution, Prenylation, Tandem reactions",

author = "Kodet, {John G.} and Topczewski, {Joseph J.} and Gardner, {Kevyn D.} and Wiemer, {David F.}",

note = "Funding Information: Financial support from the ACS Division of Medicinal Chemistry (in the form of a predoctoral fellowship to J.J.T.), the University of Iowa Graduate College (in the form of a Presidential Fellowship to J.G.K.), the Roy J. Carver Charitable Trust , and the National Cancer Institute ( R41CA126020 via Terpenoid Therapeutics, Inc.) is gratefully acknowledged. ",

year = "2013",

month = nov,

day = "4",

doi = "10.1016/j.tet.2013.08.056",

language = "English (US)",

volume = "69",

pages = "9212--9218",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier Limited",

number = "44",

}

TY - JOUR

T1 - Electrophilic aromatic prenylation via cascade cyclization

AU - Kodet, John G.

AU - Topczewski, Joseph J.

AU - Gardner, Kevyn D.

AU - Wiemer, David F.

N1 - Funding Information: Financial support from the ACS Division of Medicinal Chemistry (in the form of a predoctoral fellowship to J.J.T.), the University of Iowa Graduate College (in the form of a Presidential Fellowship to J.G.K.), the Roy J. Carver Charitable Trust , and the National Cancer Institute ( R41CA126020 via Terpenoid Therapeutics, Inc.) is gratefully acknowledged.

PY - 2013/11/4

Y1 - 2013/11/4

N2 - To gain access to prenylated hexahydroxanthenes, tandem cascade cyclization-electrophilic aromatic substitution reactions have been studied on substrates bearing allylic and propargylic substituents. Both BF 3·OEt2 and TMSOTf can be used to initiate this reaction sequence, resulting in different ratios of the C-2 and C-6 substitution products. Even though allylic transposition is observed in some cases, the results of a crossover experiment are consistent with an intramolecular reaction sequence. Taken together, these studies now allow preparation of either the C-2 or C-6 prenylated hexahydroxanthene products.

AB - To gain access to prenylated hexahydroxanthenes, tandem cascade cyclization-electrophilic aromatic substitution reactions have been studied on substrates bearing allylic and propargylic substituents. Both BF 3·OEt2 and TMSOTf can be used to initiate this reaction sequence, resulting in different ratios of the C-2 and C-6 substitution products. Even though allylic transposition is observed in some cases, the results of a crossover experiment are consistent with an intramolecular reaction sequence. Taken together, these studies now allow preparation of either the C-2 or C-6 prenylated hexahydroxanthene products.

KW - Cationic

KW - Cyclization

KW - Electrophilic aromatic substitution

KW - Prenylation

KW - Tandem reactions

UR - http://www.scopus.com/inward/record.url?scp=84884413287&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84884413287&partnerID=8YFLogxK

U2 - 10.1016/j.tet.2013.08.056

DO - 10.1016/j.tet.2013.08.056

M3 - Article

AN - SCOPUS:84884413287

SN - 0040-4020

VL - 69

SP - 9212

EP - 9218

JO - Tetrahedron

JF - Tetrahedron

IS - 44

ER -

Electrophilic aromatic prenylation via cascade cyclization

Abstract

Bibliographical note

Keywords

Access

OpenUrl availability

Other files and links

Fingerprint

Cite this