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NaBH4 Reduction of Ketones in the Solid State.

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drying under vacuum, extraction with hexane and crystallization at -30°C
afforded 300 mg (0.64 mmol; 20% referred to 5 ) of deep-red, light- and airsensitive needles of 3. M.p. 143°C (decomp.), soluble even in pentane.-'H
NMR (80 MHz, CDCI,, int. TMS): 6=7.67 (m,2H,), 7.35 (m,2H,,+H,),
~ ~"B
=~.~
4.18 (s, Cp), 4.93 (m, H-3,4), 3.72 (m, H-2,5); I V = . ~ J ~ , + ~ JHz.
NMR (32.08 MHz, CDC13, ext. BF3.0Et2):6= 13.8. ''C NMR (67.88 MHz,
CDCI,, -70°C): 6=251.6 (s, CO), 141.4 (s, C,), 132.9 (dm, 'JCH=157 Hz,
= Hz, Cm), 127.2 (dt, ' J C H = 160 Hz, C,,), 69.9 (dm,
C,,), 127.7 (dd, ' J c H 154
IJC.H= 177 Hz, Cp), 66.4 (d, 'JcH=167 Hz, C-2.51, 66.2 (d, ' J C H = 183 Hz,
C-3,4).
4 : Synthesis and work-up as described for 3; 1.95 g (3.05 mmol)
[Na10(CH2CH20Me)212][Ta(CO)61,
0.60 g (6.1 mmol) CuCl and 0.79 g (3.02
mmol) 5 give 430 mg (0.78 mmol; 26% referred to 5 ) deep-red, almost airstable needles of 4. M.p. 164°C (decomp.), soluble even in pentane.--'H
NMR (80 MHz, CDCI,, int. TMS): S=7.66 (m, 2H,), 7.34 (m,2H,+H,),
4.21 (s, Cp), 4.85 (m, H-3,4), 3.63 (m, H-2.5); N = 3J23+4J24=3.9Hz. "B
NMR (32.08 MHz, CDCI,, ext. BF3.0Etz): 6 = 12.8. "C NMR (67.88 MHz,
CDCI,, -7O'C): 6=246.7 (s, CO), 140.6 (s, C,), 133.0 (dm, IJCH=157 Hz,
C,,), 127.8 (dd, 'JCH=
160 Hz, C,,,), 127.4 (dt, ' J C H =154 Hz, Cp), 70.9 (dm,
' J c H = 178 Hz, Cp), 64.3 (d, 'JcH=
156 Hz, C-2,5), 64.7 (d, ' J C H = 190 Hz,
C-3,4).
Received: September 6, 1988;
revised: November 28, 1988 [ Z 2957 IE]
German version: Angew. Chem. 101 (1989) 328
CAS Registry numbers:
1, 118657-21-9; 2, 118657-22-0; 3, 118657-23-1; 4, 118657-24-2; 5, 103432.559; 6, 118657-25-3; 7, 84821-59-0; 8, 118657-26-4; V(CO)6, 14024-00-1;
[NaiO(CH2CH20Me)2)2][Nb(CO)61, 12189-43-4; [NajO(CH,CH20Me)2)2][Ta(CO),]. 12 189-44-5; I-phenyl-2,s-dihydro- 1 H-borole, 84017-49-2.
[I] G. E. Herberich, U. Biischges, Chem. Ber.. in press.
121 For further references see: a) W. Siebert, Angew. Chem. 97 (1985) 924;
Angew. Chem. Int. Ed. Engl. 24 (1985) 943; b) 0. J. Scherer, J. Schwalb,
H. Swarowsky, G. Wohnershauser, W. Kaim, R. Gross, Chem. Ber. 121
(1988) 443.
(31 a) A. W. Duff, K. Jonas, J. Am. Chem. SOC.105 (1983) 547; b) P. T.
Chesky, M. B. Hall, ibid. 106 (1984) 5186: c) K. Angermund, K. H.
Claus, R. Goddard, C. Kriiger, Angew. Chem. 97 (1985) 241; Angew.
Chem. Int. Ed. Engl. 24 (1985) 237; d) K. Jonas, W. Riisseler, K. Angermund, C. Kriiger, ibid. 98 (1986) 904 and 25 (1986) 927.
141 H. Werner, A. Salzer, Synfh. Inorg. Met. Org. Chem. 2 (1972) 239; A.
Salzer, H. Werner, Angew. Chem. 84 (1972) 949: Angew. Chem. Int. Ed.
Engl. I 1 (1972) 930; Synth. Inorg. Met. Org. Chem. 2 (1972) 249; H.
Werner, B. Ulrich, A. Salzer, J. Organornet. Chem. 141 (1977) 339; E.
Dubler, M. Textor, H. R. Oswald, G. B. Jameson, Acfa Crystallogr. Sect.
8 3 9 (1983) 607.
[5] a) J. W. Lauher, M. Elian, R. H. Summerville, R. Hoffmann, J . Am.
Chem. Soc. 98 (1976) 3219; b) K. Wade, Adv. Inorg. Chem. Radiochem.
18 (1976) 1; c) further theoretical studies: [3b]; E. D. Jemmis, A. C. Reddy, Organometallics 7 (1988) 1561.
161 G. E. Herberich, B. Hessner, D. P. J. Koffer, J. Organornet. Chem. 362
(1989) 243.
[7] F. Calderazzo, G. Pampaloni, J. Organornet. Chem. 303 (1986) 1 I I.
[8] Correct C,H analyses. The molecular ions and successive cleavage of 8
(in the case of 1) and 4 (in the case of 2-4) CO groups are observed in
the mass spectra.
191 G. E. Herberich, B. Hessner, R. Saive, Organomel. Chem. 319 (1987) 9.
[lo] a) G. E. Herberich, B. Hessner, J. A. K. Howard, D. P. J. Koffer, R.
Saive, Angew. Chem. 98 (1986) 177; Angew. Chem. Inr. Ed. Engl. 25
(1986) 165; b) G. E. Herberich, K. Peters, unpublished.
NaBH, Reduction of Ketones in the Solid State
By Fumio Toda,* Koji Kiyoshige, and Minoru Yagi
Previously we reported that Baeyer-Villiger oxidations
of ketones with rn-chloroperbenzoic acid proceed much
faster in the solid state than in solution."] We have now
found that reductions of ketones with NaBH, also proceed
in the solid state (Table 1). In addition, the formation of
1 : 1 inclusion complexes can be exploited to carry out regio- and enantioselective reductions leading to products
[*I
Prof. F. Toda, K. Kiyoshige, M. Yagi
Department of Industrial Chemistry, Faculty of Engineering
Ehime University, Matsuyama 790 (Japan)
320
0 VCH Veriagsgeseiischaji mbH, 0-6940 Weinheim, 1989
such as 2a and 4, which are of interest as synthetic building blocks but only accessible with difficulty by other
routes.
A mixture of the ketone and a tenfold molar amount of
NaBH4 was finely powdered using an agate mortar and
pestle and kept in a dry box at room temperature for five
days, being stirred once a day. The reaction mixture was
extracted with ether, and the dried ether solution was
evaporated to give the corresponding alcohol in the yields
shown in Table 1. Almost the same results were obtained
by shaking the mixture for a day using a test-tube shaker.
Table 1. Reduction of simple ketones in the solid state by NaBH.,.
Ketone
Alcohol
Yield
Ph2CH-OH
Ph2C0
trans- PhCH=CHCOPh
[Oh]
100
trans- PhCH=CHCHPh
100 (1 : 1)
PhCH2CH2CHPh
I
OH
B r n C O P h
B r eC HIP h
100
OH
53
m
C
O
M
e
PhCHCOPh
I
OH
meso -PhCH-CHPh
PhCH2COPh
PhCH2CHPh
I
OH
62
1
OH
63
I
OH
OH
tB"C)-;O
t B u e 0 H
92
PhCOCONiPr2
PhCHCONiPr2
24
I
OH
Treatment of a 1 : 1 inclusion ~ o m p l e x l *of
, ~ ~(R)-1 and
(R,R)-5 with NaBH4 in the solid state for 3 days gave
(R,R)-2a of 100% ee ([a],-192.8 (c=0.24, benzene)) in
54%yield. The corresponding reaction of a 1 :1 complex of
(S)-1 and (S,S)-5 gave (S,S)-2a of 100% ee. Treatment of
the racemic diketone 1 with (R,R)-5 results in selective
formation of an inclusion complex with (R)-1 : decomposition of the complex gives (R)-1 of 100% ee. Since the hydride attacks the carbonyl carbon at the 7-position from
the side opposite the methyl group,14] (R)-1 should give
(R,R)-2a of 100% ee, as was found. The IR spectrum and
[a],value of the product were comparable to those of an
authentic sample ([a],- 203 (c= 1.545, benzene)) prepared
by biological reduction of rac-1 .Is1
The enone moiety of (R)-1 is presumably masked by
forming a hydrogen bond with the hydroxyl group of
( R , R ) - 5 ,so that the other carbonyl group is reduced selectively. When the reduction of (R)-1 is carried out in the
presence of (R,R)-5 in a suspension in water, the diol 2b is
obtained as a mixture of diastereomers.
0570-0833/89/0303-0320 $ 02.50/0
Angew. Chem. Int. Ed. Engl. 28 (1989) No. 3
&
OH
OH
Me:
0
(R,R)-(-)-2a
2b
In the course of our investigations of the reactivity of
[Fe,(CO)&-CF),] 217]towards alkynes,''' we have discovered a novel type of reaction. Thus, reaction of 1 with 2
proceeds with coupling of both CF ligands to the phosphaalkyne to afford the five-membered phosphaferra heterocycle of complex 3.
t Bu
It is not easy to prepare even racemic alcohol rac-2a.
Recently, a preparative synthesis of ruc-2a by selective reduction of rac-1 with NaBH4 in MeOH/ClCH2CH2Cl
(1 : 1) at - 78 "C was reported.[41A more complicated preparative method is the Mn02 oxidation of ruc-2b, prepared
by reduction of ruc-1 .[61 The above-mentioned biological
method is also cornpli~ated.'~~
Similar reduction of a 1 :1 complex[31of (R)-3 and
(R,R)-5 with NaBH4 in the solid state gave (R,R)-4 of
100% ee ([a]D -98.2 (c=0.3, benzene) in 55% yield. The
[a]D value is comparable to that recorded for an authentic
sample ([a]D -97 (c= 1.415, benzene) prepared by a biological rnethod.l']
Received: September 14, 1988;
supplemented: November 17, 1988 [Z 2967 IE]
German version: Angew. Chem. 101 (1989) 329
[I] F. Toda, M. Yagi, K. Kiyoshige, J. Chem. SOC.Chem. Commun. 1988,
958.
[2] Some alcohol host compounds such as 5 form inclusion complexes with
a wide variety of guest compounds and form crystalline inclusion compounds with a stoichiometric host :guest ratio: F. Toda, Top. Curr. Chem.
140 (1987)43, 149(1988) 211.
[3] F. Toda, K. Tanaka, Tetrahedron Lett. 29 (1988) 551.
[4] D. E. Ward, C. K. Rhee, W. M. Zoghaib, Tetruhedron Letf. 29 (1988)
517.
[5] V. Prelog, W. Acklin, Helu. Chim. Acta 39 (1956) 748.
[6] F. Sondheimer, D. Elad, J. Am. Chem. SOC.79 (1957) 5542.
171 W. Acklin, V. Prelog, A. P. Prieto, Helu. Chim. Acta 41 (1958) 1416.
Formation of a PhosphaferracyclopentadieneRing
by Coupling of a Phosphaalkyne with Two
Fluoromethylidyne Ligands**
By Dieter Lentz* and Heike Michael
The coordination chemistry of the phosphaalkyne
tBuC=P 1[']has been extensively investigated in the last
few years.I2] Other reactions that have been reported recently for 1 include its cyclodimerization and cyclotrimerization,13] [2 + 21-, [3 21- and [4 2]-cy~loadditions,[~l
dimerization with insertion of CO,''] as well as a reaction
with a Fischer-type carbene complex.[61
+
+
[*] Priv.-Doz. Dr. D. Lentz, Dip1.-Chem. H. Michael
lnstitut fur Anorganische und Analytische Chemie
der Freien Universitat
Fabeckstrasse 34-36, D-1000Berlin 33
[**I This work was supported by the Fonds der Chemischen Industrie, the
Deutsche Forschungsgemeinschaft and the BASF AG (donation of pentacarbonyliron). We thank Prof. J . Fuchs for assistance with the crystal
structure investigation and DipLChem. L. Turowsky for providing the
compound fBuC-P.
Angew. Chem. Inr. Ed. Engl. 28 (1989) No. 3
I
F
2
3
The "F NMR spectrum of 3 exhibits two doublets and
the 31PNMR spectrum contains a doublet of doublets (Table 1).
Table I. Spectroscopic data for the compounds 3 and 5a-c.
3: IR (n-pentane): ?=2078 (s), 2033 (vs), 1994 (s), 1877 (m), 1861 (m) c m - ' ;
I9F NMR (CDC13, CFCL ext. standard): 6= -68.7 ('JPF=24 Hz), -99.5
( 2 J ~ ~ = 6Hz);
1 "P NMR (CDCI,, H,P04 ext. standard): 6 = 2.9 (dd); MS (80
ev): m/z 554 (M"),successive CO cleavage and further smaller fragment
ions, high resolution of the molecular ion peak: calcd. 553.8051, found
553.8046
Sa:IR(n-pentane): ?=2071 (w),2038(~),201O(w),1986(vs), 1956(m)cm-';
I9F NMR (CDCI,, CFCI, ext. standard): 6 = -67.6 ('JPF= 17 Hz), - 100.4
( 2 J ~ ~ = 3Hz);
4 "P NMR (CDCI3, H,PO, ext. standard): 6=74.0 (dd): MS
(80 ev): m/z 746 (M"),
successive CO cleavage and additional smaller fragment ions, high resolution of the peak Ma-CO: calcd. 717.7253, found
717.7224
5b: IR (n-hexane): 5=2076 (s), 2039 (s), 2035 (m), 2026 (vs), 2001 (m),1999
(m), 1993 (w), 1983 (m), 1979 (m), 1976 (m), 1933 (m), 1929 (m), 1880 (m).
1868 (m) cm-'; 'H NMR (CD2CI2): 6=1.82 (CH,, 5JHF=2.4 Hz), 4.99
(C5H5, J P H " ~ Hz); "F NMR (CD2C12, CFCI, ext. standard): 6= -64.9
('Jr~=17.1, ' J H F = ~ . ~ Hz), -101.6 (2Jp~=30.5Hz, 4JFF=3.1 Hz); "P NMR
suc(CD2C12,H,POI ext. standard): 6= 116 (br); MS (80 ev): m / z 730 (Me),
cessive C O cleavage and further smaller fragment ions, high resolution of the
molecular ion peak: calcd. 729.7721, found 729.7726
5c: IR (n-pentane): ?=2074 (s), 2038 (s), 2023 (vs), 1996 (m), 1979 (m), 1961
(w), 1913 (m), 1876 (m), 1863 (m) c m - ' ; 'H NMR (CD2C12): &= 1.76 (CH,,
5 J ~ ~ = 2 . Hz),
4
2.03 (Cp*); I9F NMR (CD2C12, CFCI, ext. standard):
6= -65.7 ('Jr~=21.4, 5 J ~ ~ = 2 .HZ),
4 -96.6 ('Jp~=29.9 HZ, 'JFF=3.1 HZ);
"P NMR (CDZCL,H3P04ext. standard): 6=110 (br); MS (80 ev): m/z 800
(M"),successive CO cleavage and further smaller fragment ions, high resolution of the molecular ion peak: calcd. 799.8504, found 799.8516
An X-ray structure analysis"] showed that 3 has a pentagonal bipyramidal cluster skeleton (Fig. la). The fivemembered Fe-C-P-C-C ring is completely planar (maximum deviation 0.4 pm) with the two F atoms and the central C atom of the tBu group also lying in this plane (maximum deviation 0.8 pm). The near equality of the two C-P
bond lengths indicates extensive delocalization of the electrons in the five-membered ring. Assuming that the phosphorus atom contributes three skeletal electrons, the cluswhich predict this
ter 3 conforms with the Wade
type of closo structure for 16 skeletal electrons. A carbon
analogue of 3, Fe,(CO),[Fe(CPh),] (i.e., with CPh instead
of P) was synthesized by Hubel et al. in 19591"a1and was
structurally
some years later.
0 VCH Verlagsgesellschaji mbH. D-6940 Weinheim. I989
OS70-0833/89/0303-0321$ OZ.SO/O
32 1
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