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

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;

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

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Referenzen

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’:

<A NAME="RY00506ST-1A">1a</A> For Part 132, see: Marradi M. Brandi A. Magull J. Schill H. de Meijere A. Eur. J. Org. Chem. 2006, in press

<A NAME="RY00506ST-1B">1b</A> Part 131: Bagutski V. Moszner N. Zeuner F. Fischer UK. Adv. Synth. Catal. 2006, in press

<A NAME="RY00506ST-2">2</A> Tanguy C. Bertus P. Szymoniak J. Larionov OV. de Meijere A. Synlett 2006, in press (e-First, DOI: 10.1055/s-2006-941600)

The well-known vinylcyclopropane-to-cyclopentene rearrangement is significantly accelerated by donor substit-uents like alkoxy and dialkylamino groups in the 2-position; compare with:

<A NAME="RY00506ST-3A">3a</A> McGaffin G. Grimm B. Heinecke U. Michaelsen H. de Meijere A. Walsh R. Eur. J. Org. Chem. 2001, 3559 ; and references cited therein

<A NAME="RY00506ST-3B">3b</A> Voigt T. Winsel H. de Meijere A. Synlett 2002, 1362

The rearrangement of cyclopropylketimines, which is catalyzed by acids and known as the Cloke rearrangement, should also be accelerated by donor substituents:

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<A NAME="RY00506ST-4B">4b</A> Review: Hudliky T. Becker DA. Fan RL. Kozhushkov SI. In Methods of Organic Chemistry, Houben-Weyl Vol. E17c: de Meijere A. Thieme; Stuttgart: 1997. p.2538

<A NAME="RY00506ST-4C">4c</A> See also: Funke C. Es-Sayed M. de Meijere A. Org. Lett. 2000, 2: 4249 ; and references cited therein

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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).

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.

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