4216 J . Org. Chem., Vol. 64, No. 11, 1999
Additions and Corrections
Sm(OTf)3,15 SmI2,16 and SmI3 were prepared according to
literature procedures.
17
along with cyclohexanoneoxime (16) (eq 4). However, Sm-
(OiPr)3 promoted the hydrolysis of oxime acetate 14 to
oxime 16 rather than the addition of hydrogen cyanide.
Compound 15 is an attractive precursor of an R-amino
acid. The present lanthanide-catalyzed hydrocyanation
of oxime ester provides an alternative route for the
synthesis of R-acetylaminonitrile, although the optimum
reaction conditions must be further investigated.
Gen er a l P r oced u r e for th e Cp *2Sm (th f)2-Ca ta lyzed Ace-
tylcya n a tion of Ald eh yd es w ith Aceton e Cya n oh yd r in a n d
Isop r op en yl Aceta te. To a Schlenk tube containing a toluene
solution (1 mL) of Cp*2Sm(thf)2 (0.1 mmol) were added aldehydes
(1 mmol), acetone cyanohydrin (1 mmol), and isopropenyl acetate
(2 mmol). The reaction mixture was stirred at room temperature
for 15 h under argon. After the reaction, wet diisopropyl ether
was added to the solution, and the catalyst was removed by
filtration. Removal of the solvent under reduced pressure
afforded a yellow liquid, which was purified by column chroma-
tography on silica gel with n-hexane/ethyl acetate (10/1 v/v) as
eluent to give the corresponding acetates.
2-Acetoxybu tyr on itr ile (2b):18 1H NMR (CDCl3) δ 1.11 (t,
J ) 7.4 Hz, 3H), 1.89-2.05 (m, 2H), 2.14 (s, 3H), 5.28 (t, J ) 6.6
Hz, 1H); 13C NMR (CDCl3) δ 8.9, 20.3, 25.8, 62.2, 116.7, 169.2.
2-Acetoxyisova ler on itr ile (2c): 1H NMR (CDCl3) δ 1.08 (d,
J ) 6.8 Hz, 3H), 1.12 (d, J ) 6.8 Hz, 3H), 2.10-2.25 (m, 1H),
2.16 (s, 3H), 5.18 (d, J ) 5.1 Hz, 1H); 13C NMR (CDCl3) δ 17.3,
17.7, 20.3, 31.0, 66.3, 116.0, 169.2.
2-Aetoxy-4-m eth ylva ler on itr ile (2d ): 1H NMR (CDCl3) δ
0.98 (d, J ) 6.5 Hz, 3H), 0.99 (d, J ) 6.5 Hz, 3H), 1.76-1.90 (m,
3H), 2.13 (s, 3H), 5.36 (t, J ) 7.3 Hz, 1H); 13C NMR (CDCl3) δ
20.3, 22.0, 22.1, 24.4, 40.7, 59.8, 117.0, 169.1.
2-Aetoxy-3,3-d im eth ylbu tyr on itr ile (2e): 1H NMR (CDCl3)
δ 1.15 (s, 9H), 2.22 (s, 3H), 5.12 (s, 1H); 13C NMR (CDCl3) δ
20.1, 25.0, 34.5, 69.2, 115.9, 169.1.
In conclusion, we found a direct acetylcyanation method
of aldehydes with AC in the presence of IPA catalyzed
by Cp*2Sm(thf)2 under mild conditions. R,â-Unsaturated
carbonyl compounds produced Michael addition products
under neutral conditions.
1
2-Aetoxy-2-cycloh exyla ceton itr ile (2f): H NMR (CDCl3)
δ 1.12-1.32 (m, 5H), 1.67-1.93 (m, 6H), 2.14 (s, 3H), 5.18 (d, J
) 7.3 Hz, 1H); 13C NMR (CDCl3) δ 20.3, 25.2, 25.3, 25.7, 27.8,
28.0, 40.0, 65.5, 116.1, 169.2.
2-Aetoxy-2-p h en yla ceton itr ile (2g): 1H NMR (CDCl3) δ
2.16 (s, 3H), 6.41 (s, 1H), 7.44-7.53 (m, 5H); 13C NMR (CDCl3)
δ 20.4, 62.8, 116.1, 127.8, 129.2, 130.3, 131.7, 168.9.
2-Hyd r oxy-4-cya n oh ep ta n en itr ile (2i): 1H NMR (CDCl3)
δ 0.99 (t, J ) 6.8 Hz, 3H), 1.36-1.78 (m, 4H), 2.05-2.14 (m,
2H), 2.88-3.02 (m, 1H), 3.15-3.22 (m, 1H), 4.65-4,80 (m, 1H);
13C NMR (CDCl3) δ 13.3, 20.1, 27.1, 33.7, 36.9, 58.0, 119.2, 120.7.
1-Cya n o-N-cycloh exylh yd r oxya m in e O-a ceta te (15): 1H
NMR (CDCl3) δ 1.18-2.08 (m, 10H), 2.11 (d, J ) 2.7 Hz, 3H),
7.58 (s, 1H); 13C NMR (CDCl3) δ 18.7, 21.7, 27.1, 24.6, 32.9, 59.4,
119.9, 169.9.
Exp er im en ta l Section
Gen er a l P r oced u r e. 1H and 13C NMR spectra were mea-
sured at 270 and 67.5 MHz, respectively, in CDCl3 with TMS
as the internal standard. IR spectra were measured as thin films
on NaCl plates or KBr pressed disks. GLC analysis was
performed with a flame ionization detector using a 1 mm × 30
m capillary column (OV-1). Mass spectra were determined at
an ionizing voltage of 70 eV. Isopropenyl acetate and acetone
cyanohydrin were purchased from a commercial origin and
distilled prior to use. Cp*2Sm(thf)2,13 Cp*2Yb(thf)2,13 Sm(OiPr)3,14
Ack n ow led gm en t. This work is supported by a
Grant-in-Aid for Scientific Research (No. 10132262) on
Priority Areas (No. 283), “Innovative Synthetic Reac-
tins” from Monbusho.
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Additions and Corrections
Vol. 64, 1999
Br u n o Lin cla u , Ash va n i K. Sin g, a n d Den n is P .
Cu r r a n *. Organic-Fluorous Phase Switches: A Fluorous Amine
Scavenger for Purification in Solution Phase Parallel Syn-
thesis.
Page 2835. Ashvani K. Sing’s surname should be
spelled Singh.
J O9949873
10.1021/jo9949873
Published on Web 05/04/1999