The influence of benzylic protection and allylic substituents on the CuCl-TMEDA catalyzed rearrangement of N-allyl-N-benzyl-2,2-dihaloamides to gamma-lactams. Application to the stereoselective synthesis of pilolactam.

F  Ghelfi; F  Bellesia; L  Forti; G  Ghirardini; R  Grandi; E  Libertini; M C  Montemaggi; U M  Pagnoni; A  Pinetti; L  De Buyck; A F  Parsons

The influence of benzylic protection and allylic substituents on the CuCl-TMEDA catalyzed rearrangement of N-allyl-N-benzyl-2,2-dihaloamides to gamma-lactams. Application to the stereoselective synthesis of pilolactam.

F Ghelfi, F Bellesia, L Forti, G Ghirardini, R Grandi, E Libertini, M C Montemaggi, U M Pagnoni, A Pinetti, L De Buyck, A F Parsons

Chemistry

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

Abstract

A number of N-benzylic protecting groups and allylic substituents have been investigated for the rearrangement, promoted by CuCl-TMEDA, of N-allyl-2,2-dihaloamides to 3,4-disubstituted gamma-lactams. An appreciable chiral induction was observed at the C-4 site when alpha-phenylethylamine was used as a chiral protecting group, while an unexpected Diels-Alder reaction occurred when using a 2-furyl-methyl protection. This rearrangement has been applied to the synthesis of pilolactam, a drug with muscarinic activity. (C) 1999 Elsevier Science Ltd. All rights reserved.

Original language	English
Pages (from-to)	5839-5852
Number of pages	14
Journal	Tetrahedron
Volume	55
Issue number	18
Publication status	Published - 30 Apr 1999

Keywords

radicals and radical reactions
cyclisation
pyrrolidinones
lactams
RADICAL CYCLIZATIONS
N-ALLYLTRICHLOROACETAMIDES
AMIDES
TEMPERATURE
AMINES
ESTERS

Cite this

Ghelfi, F., Bellesia, F., Forti, L., Ghirardini, G., Grandi, R., Libertini, E., Montemaggi, M. C., Pagnoni, U. M., Pinetti, A., De Buyck, L., & Parsons, A. F. (1999). The influence of benzylic protection and allylic substituents on the CuCl-TMEDA catalyzed rearrangement of N-allyl-N-benzyl-2,2-dihaloamides to gamma-lactams. Application to the stereoselective synthesis of pilolactam. Tetrahedron, 55(18), 5839-5852.

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title = "The influence of benzylic protection and allylic substituents on the CuCl-TMEDA catalyzed rearrangement of N-allyl-N-benzyl-2,2-dihaloamides to gamma-lactams. Application to the stereoselective synthesis of pilolactam.",

abstract = "A number of N-benzylic protecting groups and allylic substituents have been investigated for the rearrangement, promoted by CuCl-TMEDA, of N-allyl-2,2-dihaloamides to 3,4-disubstituted gamma-lactams. An appreciable chiral induction was observed at the C-4 site when alpha-phenylethylamine was used as a chiral protecting group, while an unexpected Diels-Alder reaction occurred when using a 2-furyl-methyl protection. This rearrangement has been applied to the synthesis of pilolactam, a drug with muscarinic activity. (C) 1999 Elsevier Science Ltd. All rights reserved.",

keywords = "radicals and radical reactions, cyclisation, pyrrolidinones, lactams, RADICAL CYCLIZATIONS, N-ALLYLTRICHLOROACETAMIDES, AMIDES, TEMPERATURE, AMINES, ESTERS",

author = "F Ghelfi and F Bellesia and L Forti and G Ghirardini and R Grandi and E Libertini and Montemaggi, {M C} and Pagnoni, {U M} and A Pinetti and {De Buyck}, L and Parsons, {A F}",

year = "1999",

month = apr,

day = "30",

language = "English",

volume = "55",

pages = "5839--5852",

journal = "Tetrahedron",

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Ghelfi, F, Bellesia, F, Forti, L, Ghirardini, G, Grandi, R, Libertini, E, Montemaggi, MC, Pagnoni, UM, Pinetti, A, De Buyck, L & Parsons, AF 1999, 'The influence of benzylic protection and allylic substituents on the CuCl-TMEDA catalyzed rearrangement of N-allyl-N-benzyl-2,2-dihaloamides to gamma-lactams. Application to the stereoselective synthesis of pilolactam.', Tetrahedron, vol. 55, no. 18, pp. 5839-5852.

The influence of benzylic protection and allylic substituents on the CuCl-TMEDA catalyzed rearrangement of N-allyl-N-benzyl-2,2-dihaloamides to gamma-lactams. Application to the stereoselective synthesis of pilolactam. / Ghelfi, F ; Bellesia, F ; Forti, L et al.
In: Tetrahedron, Vol. 55, No. 18, 30.04.1999, p. 5839-5852.

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

TY - JOUR

T1 - The influence of benzylic protection and allylic substituents on the CuCl-TMEDA catalyzed rearrangement of N-allyl-N-benzyl-2,2-dihaloamides to gamma-lactams. Application to the stereoselective synthesis of pilolactam.

AU - Ghelfi, F

AU - Bellesia, F

AU - Forti, L

AU - Ghirardini, G

AU - Grandi, R

AU - Libertini, E

AU - Montemaggi, M C

AU - Pagnoni, U M

AU - Pinetti, A

AU - De Buyck, L

AU - Parsons, A F

PY - 1999/4/30

Y1 - 1999/4/30

N2 - A number of N-benzylic protecting groups and allylic substituents have been investigated for the rearrangement, promoted by CuCl-TMEDA, of N-allyl-2,2-dihaloamides to 3,4-disubstituted gamma-lactams. An appreciable chiral induction was observed at the C-4 site when alpha-phenylethylamine was used as a chiral protecting group, while an unexpected Diels-Alder reaction occurred when using a 2-furyl-methyl protection. This rearrangement has been applied to the synthesis of pilolactam, a drug with muscarinic activity. (C) 1999 Elsevier Science Ltd. All rights reserved.

AB - A number of N-benzylic protecting groups and allylic substituents have been investigated for the rearrangement, promoted by CuCl-TMEDA, of N-allyl-2,2-dihaloamides to 3,4-disubstituted gamma-lactams. An appreciable chiral induction was observed at the C-4 site when alpha-phenylethylamine was used as a chiral protecting group, while an unexpected Diels-Alder reaction occurred when using a 2-furyl-methyl protection. This rearrangement has been applied to the synthesis of pilolactam, a drug with muscarinic activity. (C) 1999 Elsevier Science Ltd. All rights reserved.

KW - radicals and radical reactions

KW - cyclisation

KW - pyrrolidinones

KW - lactams

KW - RADICAL CYCLIZATIONS

KW - N-ALLYLTRICHLOROACETAMIDES

KW - AMIDES

KW - TEMPERATURE

KW - AMINES

KW - ESTERS

M3 - Article

SN - 0040-4020

VL - 55

SP - 5839

EP - 5852

JO - Tetrahedron

JF - Tetrahedron

IS - 18

ER -