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DOI: 10.1055/s-0029-1219223
Cyclobutylmagnesium Carbenoids: Generation from 1-Chlorocyclobutyl p-Tolyl Sulfoxides with Ethylmagnesium Chloride, Properties, and Some Synthetic Uses
Publication History
Publication Date:
04 January 2010 (online)
Abstract
Treatment of 1-chlorocyclobutyl p-tolyl sulfoxides with ethylmagnesium chloride at low temperature gave cyclobutylmagnesium carbenoids in over 90% yield. The generated magnesium carbenoids were found to be stable at -78 ˚C for at least 30 min. The synthesis of multisubstituted cyclobutanes and alkylidenecyclobutanes was realized based on the alkylation of the magnesium carbenoids with Grignard reagent and lithium α-sulfonyl carbanions, respectively.
Key words
magnesium carbenoid - cyclobutylmagnesium carbenoid - cyclobutane - alkylidenecyclobutane - sulfoxide-magnesium exchange reaction
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References and Notes
Multisubstituted
Cyclobutane 4c
A solution of EtMgCl (2.0 M solution
in THF, 0.5 mL, 1.0 mmol) was added to a solution of 1a (105
mg, 0.2 mmol) in THF (4 mL) at -78 ˚C with stirring
under Ar atmosphere. The reaction mixture was slowly allowed to
warm to 0 ˚C. To the reaction mixture was successively
added Cu(I) iodide (4 mg, 0.01 mmol) and allyl iodide (0.09 mL,
1 mmol), and the reaction mixture was stirred at 0 ˚C for
1 h. The reaction was quenched by adding sat. aq NH4Cl,
and the whole was extracted with CHCl3. The product was
purified by silica gel column chromatography to give 4c (54
mg, 64%) as colorless oil. IR (neat): 3027, 2923, 2855,
1639, 1603, 1455, 1112, 699 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 0.76 (3 H, t, J = 7.4 Hz),
1.48 (2 H, q, J = 7.4
Hz), 1.61, 1.68 (each 2 H, d, J = 12.6
Hz), 1.81-1.94 (4 H, m), 2.22 (2 H, d, J = 7.2 Hz),
2.60-2.72 (4 H, m), 3.37-3.46 (8 H, m), 4.94-5.06 (2 H, m),
5.65-5.79 (1 H, m), 7.15-7.29 (10 H, m). MS: m/z (%)
= 420
(10) [M+], 284 (4), 242 (13),
118 (100), 91 (96). MS: m/z calcd
for C29H40O2: 420.3028 [M];
found: 420.3027.
Synthesis of Benzylidenecyclobutane
5a
A solution of EtMgCl (2.0 M solution in THF, 0.25
mL, 0.5 mmol) was added to a solution of 1a (105
mg, 0.2 mmol) in THF (2 mL) under Ar atmosphere at -78 ˚C
with stirring to generate cyclobutylmagnesium carbenoid 2a. To another flame-dried flask, THF (1.5
mL) and n-BuLi (0.6 mmol) were successively
added. To this was added a solution of benzyl phenyl sulfone (139
mg, 0.6 mmol) in THF (0.5 mL) at 0 ˚C to give the lithium α-sulfonyl
carbanion as a light yellow solution. This solution was cooled to -78 ˚C
and transferred to the solution of the carbenoid 2a through
a cannula. The reaction mixture was stirred and slowly allowed to
warm to -20 ˚C, and the reaction was quenched with
sat. aq NH4Cl. The whole was extracted with CHCl3, and
the product was purified by silica gel column chroma-tography to
afford 5a (73.1 mg, 83%) as colorless
oil. IR (neat): 3026, 2942, 2858, 1680, 1601, 1496, 1113, 911, 742, 698
cm-¹. ¹H NMR (300
MHz, CDCl3): δ = 1.84-1.94
(4 H, m), 2.66-2.71 (6 H, m), 2.84-2.86 (2 H,
m), 3.46 (4 H, t, J = 6.3
Hz), 3.48 (4 H, s), 6.19 (1 H, m), 7.13-7.21 (7 H, m), 7.24-7.32
(8 H, m). MS: m/z (%) = 440
(7) [M+], 305 (11), 304 (50),
170 (27), 168 (30), 156 (19), 155 (100), 142 (8), 129 (12), 119
(18), 91 (93). MS: m/z calcd
for C31H36O2: 440.2715 [M];
found: 440.2708.