Three positional isomers of substituted triphenylmethanes from reactions of trityl anion with 1-acyl-2,2-dimethylaziridines

Jürgen Werry, Pen Yuan Lin, Petros Assithianakis, Helmut Stamm

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Ring opening of aziridines 4a-d in reactions with trityl anion Tr - proceeds exclusively by cleavage of the NCMe2 bond. Substitution of the benzylic carbon of Tr- leads to 'central' products 10a-d in yields of 0-5%. This is ascribed to an SN2 reaction with borderline character, as is well known from reactions of aziridines 4a-d with other nucleophiles. All remaining ring-opening reactions result from single-electron transfer (SET). This is direct SET from Tr- to aziridines 4a-c. For compound 4d (acyl = cinnamoyl), the SET reaction is of the innersphere type and proceeds via Michael addition, at least in part. Homolytic ring opening of the generated aziridino ketyls 5 forms the tertiary amidatoalkyl radicals 6. Main reaction of radicals 6a-c is transfer of a hydrogen atom from one of its two methyl groups to the generated trityl radical Tr*. Methallylamides 7 and enamides 8 are the final products. ortho-Substituted triphenylmethanes 12 and/or its olefinic precursors 13 arise in ∼20% yield. A mechanism for the formation of these unique products is proposed that first converts the radicals 6 into the corresponding carbanions 16 which undergo an SN2′ reaction with one allylic system TrCHCH=CH* of the dimer 14 of Tr*. The leaving group Tr- is eliminated from this partial structure when carbanions 16 attack the marked carbon converting it finally into the substituted ortho carbon of compounds 12. Addition of radicals 6 to Tr- is probably the way to the para-substituted triphenylmethanes 11, which arise in yields of only 0-1% from aziridines 4a,b (acyl = 4-benzoyl, pivaloyl). Higher yields of para-substituted compounds 11 are obtained from aziridines 4c (acyl = 4-phenylbenzoyl) and 4d. This is ascribed, at least for substrate 4c, to a chain reaction because ketyl 5c must be formed more rapidly than ketyls 5a,b. A substantial part of radical 6d cyclizes, ending up as the triphenylmethane compound 26 that carries a pyrrolidone ring in the para position.

Original languageEnglish
Pages (from-to)3103-3110
Number of pages8
JournalJournal of the Chemical Society, Perkin Transactions 1
Issue number24
Publication statusPublished - 1995
Externally publishedYes

Fingerprint

Aziridines
Isomers
Anions
Carbon
Electrons
Pyrrolidinones
Nucleophiles
Dimers
Hydrogen
Substitution reactions
triphenylmethane
Atoms
Substrates

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Three positional isomers of substituted triphenylmethanes from reactions of trityl anion with 1-acyl-2,2-dimethylaziridines. / Werry, Jürgen; Lin, Pen Yuan; Assithianakis, Petros; Stamm, Helmut.

In: Journal of the Chemical Society, Perkin Transactions 1, No. 24, 1995, p. 3103-3110.

Research output: Contribution to journalArticle

@article{f2dc5fb015e04986afa405720a534401,
title = "Three positional isomers of substituted triphenylmethanes from reactions of trityl anion with 1-acyl-2,2-dimethylaziridines",
abstract = "Ring opening of aziridines 4a-d in reactions with trityl anion Tr - proceeds exclusively by cleavage of the NCMe2 bond. Substitution of the benzylic carbon of Tr- leads to 'central' products 10a-d in yields of 0-5{\%}. This is ascribed to an SN2 reaction with borderline character, as is well known from reactions of aziridines 4a-d with other nucleophiles. All remaining ring-opening reactions result from single-electron transfer (SET). This is direct SET from Tr- to aziridines 4a-c. For compound 4d (acyl = cinnamoyl), the SET reaction is of the innersphere type and proceeds via Michael addition, at least in part. Homolytic ring opening of the generated aziridino ketyls 5 forms the tertiary amidatoalkyl radicals 6. Main reaction of radicals 6a-c is transfer of a hydrogen atom from one of its two methyl groups to the generated trityl radical Tr*. Methallylamides 7 and enamides 8 are the final products. ortho-Substituted triphenylmethanes 12 and/or its olefinic precursors 13 arise in ∼20{\%} yield. A mechanism for the formation of these unique products is proposed that first converts the radicals 6 into the corresponding carbanions 16 which undergo an SN2′ reaction with one allylic system TrCHCH=CH* of the dimer 14 of Tr*. The leaving group Tr- is eliminated from this partial structure when carbanions 16 attack the marked carbon converting it finally into the substituted ortho carbon of compounds 12. Addition of radicals 6 to Tr- is probably the way to the para-substituted triphenylmethanes 11, which arise in yields of only 0-1{\%} from aziridines 4a,b (acyl = 4-benzoyl, pivaloyl). Higher yields of para-substituted compounds 11 are obtained from aziridines 4c (acyl = 4-phenylbenzoyl) and 4d. This is ascribed, at least for substrate 4c, to a chain reaction because ketyl 5c must be formed more rapidly than ketyls 5a,b. A substantial part of radical 6d cyclizes, ending up as the triphenylmethane compound 26 that carries a pyrrolidone ring in the para position.",
author = "J{\"u}rgen Werry and Lin, {Pen Yuan} and Petros Assithianakis and Helmut Stamm",
year = "1995",
language = "English",
pages = "3103--3110",
journal = "Journal of the Chemical Society, Perkin Transactions 1",
issn = "1472-7781",
publisher = "Chemical Society",
number = "24",

}

TY - JOUR

T1 - Three positional isomers of substituted triphenylmethanes from reactions of trityl anion with 1-acyl-2,2-dimethylaziridines

AU - Werry, Jürgen

AU - Lin, Pen Yuan

AU - Assithianakis, Petros

AU - Stamm, Helmut

PY - 1995

Y1 - 1995

N2 - Ring opening of aziridines 4a-d in reactions with trityl anion Tr - proceeds exclusively by cleavage of the NCMe2 bond. Substitution of the benzylic carbon of Tr- leads to 'central' products 10a-d in yields of 0-5%. This is ascribed to an SN2 reaction with borderline character, as is well known from reactions of aziridines 4a-d with other nucleophiles. All remaining ring-opening reactions result from single-electron transfer (SET). This is direct SET from Tr- to aziridines 4a-c. For compound 4d (acyl = cinnamoyl), the SET reaction is of the innersphere type and proceeds via Michael addition, at least in part. Homolytic ring opening of the generated aziridino ketyls 5 forms the tertiary amidatoalkyl radicals 6. Main reaction of radicals 6a-c is transfer of a hydrogen atom from one of its two methyl groups to the generated trityl radical Tr*. Methallylamides 7 and enamides 8 are the final products. ortho-Substituted triphenylmethanes 12 and/or its olefinic precursors 13 arise in ∼20% yield. A mechanism for the formation of these unique products is proposed that first converts the radicals 6 into the corresponding carbanions 16 which undergo an SN2′ reaction with one allylic system TrCHCH=CH* of the dimer 14 of Tr*. The leaving group Tr- is eliminated from this partial structure when carbanions 16 attack the marked carbon converting it finally into the substituted ortho carbon of compounds 12. Addition of radicals 6 to Tr- is probably the way to the para-substituted triphenylmethanes 11, which arise in yields of only 0-1% from aziridines 4a,b (acyl = 4-benzoyl, pivaloyl). Higher yields of para-substituted compounds 11 are obtained from aziridines 4c (acyl = 4-phenylbenzoyl) and 4d. This is ascribed, at least for substrate 4c, to a chain reaction because ketyl 5c must be formed more rapidly than ketyls 5a,b. A substantial part of radical 6d cyclizes, ending up as the triphenylmethane compound 26 that carries a pyrrolidone ring in the para position.

AB - Ring opening of aziridines 4a-d in reactions with trityl anion Tr - proceeds exclusively by cleavage of the NCMe2 bond. Substitution of the benzylic carbon of Tr- leads to 'central' products 10a-d in yields of 0-5%. This is ascribed to an SN2 reaction with borderline character, as is well known from reactions of aziridines 4a-d with other nucleophiles. All remaining ring-opening reactions result from single-electron transfer (SET). This is direct SET from Tr- to aziridines 4a-c. For compound 4d (acyl = cinnamoyl), the SET reaction is of the innersphere type and proceeds via Michael addition, at least in part. Homolytic ring opening of the generated aziridino ketyls 5 forms the tertiary amidatoalkyl radicals 6. Main reaction of radicals 6a-c is transfer of a hydrogen atom from one of its two methyl groups to the generated trityl radical Tr*. Methallylamides 7 and enamides 8 are the final products. ortho-Substituted triphenylmethanes 12 and/or its olefinic precursors 13 arise in ∼20% yield. A mechanism for the formation of these unique products is proposed that first converts the radicals 6 into the corresponding carbanions 16 which undergo an SN2′ reaction with one allylic system TrCHCH=CH* of the dimer 14 of Tr*. The leaving group Tr- is eliminated from this partial structure when carbanions 16 attack the marked carbon converting it finally into the substituted ortho carbon of compounds 12. Addition of radicals 6 to Tr- is probably the way to the para-substituted triphenylmethanes 11, which arise in yields of only 0-1% from aziridines 4a,b (acyl = 4-benzoyl, pivaloyl). Higher yields of para-substituted compounds 11 are obtained from aziridines 4c (acyl = 4-phenylbenzoyl) and 4d. This is ascribed, at least for substrate 4c, to a chain reaction because ketyl 5c must be formed more rapidly than ketyls 5a,b. A substantial part of radical 6d cyclizes, ending up as the triphenylmethane compound 26 that carries a pyrrolidone ring in the para position.

UR - http://www.scopus.com/inward/record.url?scp=37049069879&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=37049069879&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:37049069879

SP - 3103

EP - 3110

JO - Journal of the Chemical Society, Perkin Transactions 1

JF - Journal of the Chemical Society, Perkin Transactions 1

SN - 1472-7781

IS - 24

ER -