Convenient Access to 2-Arylpyrroles from 2-Lithio-N,N-dibenzylcyclopropylamine and Nitriles

Chloé Tanguy; Philippe Bertus; Jan Szymoniak; Oleg V. Larionov; Armin de Meijere

doi:10.1055/s-2006-950410

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Synlett 2006(14): 2339-2341
DOI: 10.1055/s-2006-950410

CLUSTER

Convenient Access to 2-Arylpyrroles from 2-Lithio-N,N-dibenzylcyclopropylamine and Nitriles [1]

Chloé Tanguy^a,b, Philippe Bertus^a, Jan Szymoniak*^a, Oleg V. Larionov^b, Armin de Meijere*^b
^a Réactions Sélectives et Applications, CNRS (UMR6519) and Université de Reims, 51687 Reims Cedex 2, France
Fax: +33(3)26913431; e-Mail: jan.szymoniak@univ-reims.fr;
^b Institut für Organische und Biomolekulare Chemie der Georg-August-Universität Göttingen, Tammannstrasse 2, 37077 Göttingen, Germany
Fax: +49(551)399475; e-Mail: Armin.deMeijere@chemie.uni-goettingen.de;

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Publication History

Received 8 May 2006
Publication Date:
24 August 2006 (online)

Abstract
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Abstract

N,N-Dibenzylaminocyclopropyl ketimines formed as intermediates upon treatment of 2-lithiated N,N-dibenzylcyclopropylamines with nitriles, being donor-acceptor-substituted cyclopropanes, immediately underwent ring-enlarging rearrangement and 1,2-elimination of dibenzylamine to produce 2-substituted pyrroles in good yields (14 examples, 55-80%).

Key words

tin-lithium exchange - nitriles - 2-arylpyrroles - cyclopropylamines - donor-acceptor-substituted cyclopropanes

References and Notes

For one of us (A.d.M.) this is to be counted as Part 133 in the series, ‘Cyclopropyl Building Blocks for Organic Synthesis’:
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Typical Procedure. To a solution of trans-2-(tributylstan-nyl)-N,N-dibenzylcyclopropylamine (3, 526 mg, 1 mmol) in THF (3 mL) was added n-BuLi (1.2 mmol, 2 M in hexane) at -30 °C. After stirring for 30 min at -30 °C, the respective nitrile (1.2 mmol) was added. The mixture was warmed to 0 °C within 2 h. At this stage, the reaction was quenched with AcOH (2 M in THF, 0.5 mL), the mixture extracted with EtOAc, the extracts dried over MgSO₄, filtered, and concentrated. The crude product was purified by flash chromatography on silica gel (PE-EtOAc, 9:1).

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2-Phenyl-1 H -pyrrole ( 10a). ¹H NMR (250 MHz, CDCl₃): d = 6.24 (br s, 1 H), 6.46 (br s, 1 H), 6.79 (br s, 1 H), 7.13 (br s, 1H), 7.21-7.32 (m, 2 H), 7.35-7.41 (m, 2 H), 8.36 (br s, 1 H, NH). ¹³C NMR (63 MHz, CDCl₃): d = 105.9, 110.1, 118.8, 123.8, 126.2, 128.9, 132.6, 132.8. HRMS (ESI): m/z calcd for C₁₀H₁₀N: 144.0813 (M + H)⁺; found: 144.0811.
2- m -Tolyl-1 H -pyrrole ( 10b). ¹H NMR (250 MHz, CDCl₃): d = 6.26 (br s, 1 H), 6.44 (br s, 1 H), 6.78 (br s, 1 H), 6.96 (br s, 1 H), 7.17-7.23 (m, 3 H), 8.35 (br s, 1 H, NH). ¹³C NMR (63 MHz, CDCl₃): d = 21.5, 105.8, 110.0, 118.6, 120.9, 124.6, 127.0, 128.7, 132.2, 132.6, 138.4. HRMS (ESI): m/z calcd for C₁₁H₁₂N: 158.0970 (M + H)⁺; found: 158.0972.
2-(3-Methoxyphenyl)-1 H -pyrrole ( 10d). ¹H NMR (250 MHz, CDCl₃): d = 3.82 (s, 3 H), 6.28 (br s, 1 H), 6.51 (br s, 1 H), 6.73-6.77 (m, 1 H), 6.83 (br s, 1 H), 6.99-7.06 (m, 2 H), 7.22-7.29 (m, 1 H), 8.42 (br s, 1 H, NH). ¹³C NMR (63 MHz, CDCl₃): d = 55.2, 106.1, 109.7, 110.0, 111.5, 116.4, 118.8, 129.9, 131.9, 134.1, 160.0. HRMS (ESI): m/z calcd for C₁₁H₁₂NO: 174.0919 (M + H)⁺; found: 174.0918.