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:
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Brandi A.
Magull J.
Schill H.
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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:
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The rearrangement of cyclopropylketimines, which is catalyzed by acids and known as
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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.
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