Exploring the substrate scope of the Ru(II)-catalyzed kharasch reaction

Article abstract of DOI:10.1135/cccc20071005

The Kharasch reaction, or atom-transfer addition of polyhalogenated alkanes to alkenes is known to be catalyzed by a number of Ru(II) complexes. The easily prepared [RuCl₂(PPh₃)₃] was used to investigate the reaction scope. A number of halogenated alkanes were added to a range of alkenes with good to excellent regioselectivities.

Full text of DOI:10.1135/cccc20071005

Ru(II)-Catalyzed Kharasch Reaction
1005
EXPLORING THE SUBSTRATE SCOPE OF THE RU(II)-CATALYZED
KHARASCH REACTION
Eskender MUME, Ian J. MUNSLOW, Klas KÄLLSTRÖM and
1,
Pher G. ANDERSSON *
Department of Biochemistry and Organic Chemistry, Uppsala University,
1
Box 576, S-751 23 Uppsala, Sweden; e-mail: phera@biorg.uu.se
Received March 12, 2007
Accepted Jun e 1, 2007
Dedicated to Professor Štefan Toma on the occasion of his 70th birthday.
Th e Kh arasch reaction , or atom -tran sfer addition of polyh alogen ated alkan es to alken es is
kn own to be catalyzed by a n um ber of Ru(II) com plexes. Th e easily prepared [RuCl2(PPh 3)3]
was used to in vestigate th e reaction scope. A n um ber of h alogen ated alkan es were added to
a ran ge of alken es with good to excellen t regioselectivities.
Keywords: Atom tran sfer; Ruth en ium ; Alken es; Catalysis; Addition s; Polyh alogen ated alkan es.
The atom -transfer addition of polyhalogenated alkanes to alkenes (Schem e 1),
th e Kh arasch addition 1, is an im portan t tool in organ ic ch em istry, because
th e resultin g products m ay be tran sform ed in to a variety of fun ction al
groups2,3. In prin ciple, th is process ben efits from th e ch em ical efficien cy;
n o ch em ical waste-products are form ed4.
cat.
SCHEME 1
Gen eral catalytic Kh arasch addition of a ch loroalkan e to an alken e
Several tran sition m etal com plexes h ave been sh own to catalyze th e
anti-Markovn ikov addition of polyh alogen ated com poun ds to alken es2.
Typical drawbacks of th e Kh arasch addition are th e lim ited scope of h alo-
gen ated substrates an d com paratively h arsh reaction con dition s. Several
successful efforts in overcom in g th ese problem s h ave been publish ed. Im -
Collect. Czech. Chem. Commun. 2007, Vol. 72, No. 8, pp. 1005–1013
© 2007 Institute of Organic Chemistry and Biochemistry
doi:10.1135/cccc20071005

1006
Mume, Munslow, Källström, Andersson:
portan t am on g th em is th e [RuCl2(PPh 3)3] catalyzed reaction , first reported
by Nagai et al.5, wh ich h as been applied to a variety of syn th etically useful
reaction s6. In a m ore recen t publication , Noels et al. dem on strated th at
[Cp*RuCl(PPh 3)3] was extrem ely active in catalyzin g th e addition of CCl4
an d CHCl3 to various alken es, ach ievin g turn over n um bers (TONs) of
1600–1700 at tem peratures as low as 40 °C 7. To date, a n um ber of Ru(II)
catalysts h ave been reported possessin g superior perform an ce superior to
[RuCl2(PPh 3)3] 8–10
.
Th e ruth en ium -catalyzed Kh arasch reaction is believed to proceed via
a radical m ech an ism in th e coordin ation sph ere of th e m etal com plex2. In
th e case of [RuCl2(PPh 3)3], th e active catalyst is believed to be th e fourteen -
electron species [RuCl2(PPh 3)2], gen erated by th e dissociation of on e PPh 3
ligan d11
.
To date th ere h ave been few reports in th e literature th at h ave dealt with
th e scope an d lim itation s of th e Ru-catalyzed Kh arasch addition reaction .
We th erefore becam e in terested in in vestigatin g th e reaction scope with re-
spect to alken es an d h alogen sources. Especially in terestin g is th e addition
of α-h alo keton es an d esters to un sym m etrical olefin s, poten tially leadin g
to h igh regiospecificity in th e addition product.
RESULTS
In th e first set of experim en ts, we in vestigated th e [RuCl2(PPh 3)3] (1) cata-
lyzed addition of CCl4 (2) to various alken es (Table I). We preferred th e
[RuCl2(PPh 3)3] com plex to [Cp*RuCl(PPh 3)3] due to its easy preparation 12
.
After refluxin g a m ixture of alken e an d CCl4 in ben zen e with 1 m ole % of
[RuCl2(PPh 3)3] for 24 h , th e addition products 16–28 were obtain ed in m od-
erate to excellen t yields. As in dicated in Table I, th e regiospecificity of th e
addition product varies from good to excellen t. In th e case of term in al
olefin s (Table I, en tries 1, 2, 13), preferen tial addition of th e Cl atom to th e
m ost substituted position of th e double bon d was observed. With α,β-
un saturated alken es an d CCl4, th e Cl atom was preferen tially tran sferred
to th e ben zylic carbon . Addition of CCl4 to cyclic alken es resulted in th e
exclusive form ation of th e trans product (Table I, en tries 4–7).
We th en furth er in vestigated th e scope of th is system with th e addition
of eth yl ch loroacetate (29) an d eth yl trich loroacetate (30) to styren e (3). As
sh own in Sch em e 2, th e reaction proceeded faster with th e m ore h alo-
gen ated ester 30 givin g 60% yield (com pared to on ly 16% for 29 in 24 h ).
Usin g th e sam e reaction con dition s, we added 30 to a n um ber of alken es 4,
6, 8, 11–15 (Table II). Th e sam e regioselectivity pattern was observed usin g
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Ru(II)-Catalyzed Kharasch Reaction
1007
TABLE I
Ru(II)-catalyzed addition of CCl4 to various alken es
En try
Alken e
Producta
Regioselectivityb
Con version b (Yield), %
1
>99:1
>99:1
–
81 (80)
67 (65)
93 (90)
81 (79)
54 (50)
70 (61)
71 (67)
30 (23)
13 (10)
53 (50)
44 (42)
56 (52)
92 (91)
2
3
4
–
5
–
6
–
7
>99:1
87:13
64:36
>99:1
89:11
91:9
>99:1
8
9
10
11
12
13
a
On ly th e m ajor isom er is sh own , 1H NMR an alysis suggests predom in an t trans diastereom er
in all cases; com poun ds 16 16, 17 17, 18 18, 19 18, 20 19, 21 20, 26
.
Determ in ed by 1H NMR.
21
b
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Mume, Munslow, Källström, Andersson:
30 (Table II) as with CCl4, th e con version s for th e addition of 30, h owever,
were gen erally lower th an for th e addition of CCl4.
[Ru] 1 mol %
[Ru] 1 mol %
SCHEME 2
[RuCl2(PPh 3)3]-catalyzed addition of 29 an d 30 to 3. Con dition s: [RuCl2(PPh 3)3] 1 m ol %,
15
C6H6, 75 °C, 24 h ; com poun d 32
TABLE II
Addition of 30 to alken es 4, 6, 8, 11–15
En try
Alken e
Producta
Regioselectivityc
Con version c (Yield), %
1a
2
>99:1
62 (60)
68 (63)
96 (94)
30 (26)
69 (61)
58 (52)
36 (33)
–
3
–
4
>99:1
5
–
6
–
7
>99:1
a
b
In 1,4-dioxan e. On ly th e m ajor isom er is sh own , 1H NMR an alysis suggests predom in an t
trans diastereom er in all cases. Determ in ed by 1H NMR.
c
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Ru(II)-Catalyzed Kharasch Reaction
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Of in terest is th e reaction of 30 with cin n am yl acetate (Table II, en try 6)
wh ich resulted in n o lin ear addition product. Rath er a two-step reaction oc-
curred, form in g lacton e 38 as th e on ly product. Th is is in agreem en t with
previous fin din gs13–15. Sim ilar lacton e form ation was also observed for th e
addition of 30 to cin n am yl alcoh ol (Table II, en try 6).
With successful results from th e addition of α-h alogen ated m on oesters,
we proceeded to in vestigate th e addition of dim eth yl ch lorom alon ate (40)
to 3. Th e addition proceeded rath er slowly, givin g on ly 15% yield after 24 h
(Sch em e 3).
[Ru] 1 mol %
SCHEME 3
[RuCl2(PPh 3)3]-catalyzed Kh arasch addition of 40 to 3. Con dition s: [RuCl2(PPh 3)3] 1 m ol %,
C6H6, 75 °C, 24 h
Th e slow reaction observed in th is case in dicates th at an im portan t factor
for obtain in g h igh con version s un der th e con dition s used is th e level of
h alogen ation in th e h alogen source. Ph en acyl ch loride (42) was also suc-
cessfully added to 3, alth ough th e product 43 was form ed in a low yield,
18% (Sch em e 4).
[Ru] 1 mol %
SCHEME 4
23
Addition of 42 to 3. Con dition s: [RuCl2(PPh 3)3] 1 m ol %, C6H6, 75 °C, 24 h ; com poun d 43
CONCLUSIONS
We h ave in vestigated th e scope an d lim itation s of th e alken es th at can be
used for th is addition , an d sh own th at [RuCl2(PPh 3)3] catalyzes th e addition
of various h alogen sources to a broad ran ge of alken es, producin g substrates
of h igh syn th etic value wh ich can be furth er utilized. We h ave sh own th at
th e Ru(II)-catalyzed Kh arasch addition to alken es n eed n ot be restricted to
th e usual polyh alogen ated com poun ds, CCl4 an d eth yl trich loroacetate, as
m alon ate esters an d ph en acyl ch loride can also be used as reactan ts for th is
reaction .
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Mume, Munslow, Källström, Andersson:
EXPERIMENTAL
All substrates were purch ased from com m ercial sources an d used as received. All reaction s
were con ducted un der n itrogen with m agn etic stirrin g. 1H an d 13C NMR spectra (δ, ppm ;
J, Hz) were recorded in CDCl3 (7.26 ppm 1H, 77.0 ppm 13C), on a Varian Un ity 400 spec-
trom eter at 400 an d 100.6 MHz, respectively. In frared spectra (νm ax, cm –1) were recorded on
a Perkin –Elm er 1760 FT-IR spectrom eter. For colum n ch rom atograph y, Merck silica gel 60
(230–400 m esh ) was used.
Gen eral Procedure
Th e catalyst (1 m ol %) was weigh ed in a 10-m l roun d-bottom flask to wh ich th e alken e
(2 m m ol) dissolved in ben zen e (0.5 m l) was added. Th e ch lorin ated com poun d (10 m m ol)
was added via syrin ge an d th e reaction m ixture was stirred at 75 °C for 24 h . Th e reaction
m ixture was cooled to room tem perature an d th e solven t evaporated in vacuo. Th e resultin g
crude product was purified by flash ch rom atograph y. Com poun ds 16–21, 26, 32, 35, 37,
an d 43 were ch aracterized by com parison of th eir spectral data with th ose in th e literature.
2-Chloro-3-(trichloromethyl)cyclohexan-1-one (22). 1H NMR (CDCl3): 1.61–1.73 (m , 1 H,
CH2); 2.19–2.27 (m , 1 H, CH2); 2.33–2.42 (m , 3 H, CH2); 2.88–2.92 (m , 1 H, CH2); 3.09 (dt,
1 H, J = 14.2, 7.0, CHCCl3); 4.84 (d, 1 H, J = 2.4, -CHCl). 13C NMR (CDCl3): 22.3, 23.3, 34.6,
60.4, 60.8, 95.3, 146.1. IR (n eat): 3437 (w), 2956, 2875, 1726 (s), 1449, 1425, 945, 815, 781,
754. MS (EI), m/z (%): 249.9 (100) [M]+, 248.3 (93), 252.1 (47), 254.1 (34), 251.3 (7), 253.2 (5).
[1,3,3,3-Tetrachloro-2-(chloromethyl)propyl]benzene (23). 1H NMR (CDCl3): 3.48–3.51 (m ,
1 H, CHCCl3); 4.12 (dd, 1 H, J = 12.6, 3.3, CH2); 4.28 (dd, 1 H, J = 12.6, 5.4, CH2); 5.85 (d,
1 H, J = 2.4, -CHCl); 7.35–7.45 (m , 3 H, Ar-H); 7.57 (d, 2 H, J = 7.6, Ar-H). 13C NMR (CDCl3):
40.8, 61.3, 67.7, 100.5, 127.5, 128.8, 129.0, 139.8. IR (n eat): 1495, 1451, 1439, 823, 765,
717, 696 (s). MS (EI), m/z (%): 305.9 (100) [M]+, 307.9 (71), 303.8 (57), 309.9 (17), 308.9
(13), 307.0 (9), 304.9 (7), 311.1 (5).
4-Chloro-4-phenyl-3-(trichloromethyl)butan-2-one (24). 1H NMR (CDCl3): 2.59 (s, 3 H, Me);
4.36 (d, 1 H, J = 10, CHCCl3); 5.50 (d, 1 H, J = 10, CHCl); 7.32–7.37 (m , 3 H, Ar-H);
7.47–7.50 (m , 2 H, J = 7.6, Ar-H). 13C NMR (CDCl3): 34.0, 61.5, 73.2, 99.3, 128.8, 129.0,
129.7, 137.6, 200.9. IR (n eat): 3447 (w), 1730 (s), 1456, 1356, 1290, 1246, 813, 760, 712 (s),
696. MS (EI), m/z (%): 300.0 (100) [M]+, 298.1 (93), 302.0 (88), 301.0 (22), 304.1 (12), 298.9
(9), 302.9 (4), 305.0 (1).
3-Chloro-3-phenyl-2-(trichloromethyl)propan-1-ol (25). 1H NMR (CDCl3): 1.97 (brs, 1 H, OH);
3.33–3.36 (m , 1 H, -CHCCl3); 4.35 (dd, 1 H, J = 12.7, 3.9, -CH2); 4,43 (dd, 1 H, J = 12.7, 5.3,
-CH2); 5.79 (d, 1 H, J = 2.4, -CHCl); 7.35–7.45 (m , 3 H, Ar-H); 7.57 (d, 2 H, J = 7.5, Ar-H).
13C NMR (CDCl3): 61.9, 62.0, 66.6, 100.8, 127.5, 128.8, 129.2, 140.8. IR (n eat): 3414 (br),
1495, 1450, 1041 (s), 908, 698 (s), 731, 697. MS (EI), m/z (%): 288.0 (100) [M]+, 286.2 (91),
290.4 (73), 289.0 (30), 292.0 (12), 287.2 (8), 291.1 (6), 292.0 (1).
3-Chloro-3-phenyl-2-(trichloromethyl)acetate (27). 1H NMR (CDCl3): 1.84 (s, 3 H, H3C-C(=O)OC-);
3.44–3.47 (m , 1 H, -CHCCl3); 4.76–4.79 (m , 2 H, -CH2OC(=O)-); 5.89 (d, 1 H, J = 2.1,
Ph CHClC); 7.34–7.38 (m , 1 H, Ar-H); 7.41–7.45 (m , 2 H, Ar-H); 7.51–7.56 (m , 2 H, Ar-H).
13C NMR (CDCl3): 20.8, 60.9, 61.9, 63.7, 100.1, 127.2, 128.5, 128.6, 140.1, 170.4. IR (n eat):
1743, 1225, 1042, 762, 697. MS (EI), m/z (%): 329.6 (100) [M]+, 327.96 (88), 330.9 (56),
330.7 (38), 334.1 (31), 329.6 (10), 333.4 (6), 335.0 (3).
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Ru(II)-Catalyzed Kharasch Reaction
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1,3,3,3-Tetrachloropropyl benzoate (28). 1H NMR (CDCl3): 3.58 (dd, 1 H, J = 15.5, 2.3,
CH2CCl3); 3.81 (dd, 1 H, J = 15.5, 8.6, CH2CCl3); 7.16–7.18 (dd, 1 H, J = 8.6, 2.3, -CHCl);
7.50–7.53 (m , 2 H, Ar-H); 7.65–7.66 (m , 1 H, Ar-H); 8.13–8.15 (m , 2 H, Ar-H). 13C NMR
(CDCl3): 61.2, 79.9, 94.3, 128.5, 128.9, 130.5, 134.4, 163.8. IR (n eat): 1741, 1242, 1062,
1045, 701, 573. MS (EI), m/z (%): 301.0 (100) [M]+, 299.9 (78), 304.2 (37), 302.8 (17), 305.4
(11), 301.0 (9), 305.0 (4).
Ethyl 4-chloro-4-phenylbutanoate (31). 1H NMR (CDCl3): 1.29 (t, 3 H, J = 7.2, H3CH2OC(=O));
2.39–2.44 (m , 2 H, -CH2C(=O)O-); 2.49–2.53 (m , 2 H, -CH2CHClPh ); 4.16 (q, 2 H, J = 7.2,
CH3CH2OC(=O)-); 4.99 (dd, 1 H, J = 8.5, 6.2, Ph CHCl-); 7.34–7.43 (m , 5 H, Ar-H). 13C NMR
(CDCl3): 14.5, 31.9, 35.3, 60.8, 62.9, 127.1, 128.7, 129.0, 141.3, 172.8. IR (n eat): 1729, 1180,
1157, 761, 696. For C12H15Cl1O2 (226.7) calculated: 63.58% C, 6.67% H; foun d: 63.66% C,
6.56% H.
Ethyl 2,2,4-trichloro-5-phenylpentanoate (33). 1H NMR (CDCl3): 1.39 (t, 3 H, J = 7.1,
CH3CH2-OC(=O)-); 2.89 (dd,
Ph CH2CHCl-, -CH2CCl2-); 4.35 (q,
1
H, J = 15.1, 3.2, Ph CH2-CHCl); 3.12–3.17 (m ,
H, J = 7.1, CH3CH2-OC(=O)-); 4.45 (m ,
3
1
H,
H,
2
-CHClCH2-); 7.26–7.27 (m , 2 H, Ar-H); 7.31–7.33 (m , 1 H, Ar-H); 7.36–7.40 (m , 2 H, Ar-H).
13C NMR (CDCl3): 14.0, 45.3, 52.1, 58.3, 64.4, 83.0, 127.5, 128.9, 129.6, 136.9, 165.7. IR
(n eat): 1758, 1745, 1242, 1200, 1027, 750, 698. MS (EI), m/z (%): 313 (27), 311 (82), 310
(20), 309 (94) [M]+, 275 (37), 273 (59), 239 (19), 238 (40), 237 (53), 236 (100), 209 (23). For
C
13H15Cl3O2 (309.6) calculated: 50.43% C, 4.88% H; foun d: 51.47% C, 4.98% H.
Ethyl 2,2-dichloro-2-(2-chlorocyclohexyl)acetate (34). 1H NMR (CDCl3): 1.35–1.46 (m , 6 H,
CH2, CH2CH3); 1.71–1.85 (m , 2 H, CH2); 1.89–1.93 (m , 1 H, CH2); 2.24–2.30 (m , 1 H, CH2);
2.57–2.62 (m , 1 H, CH2); 2.80–2.87 (m , 1 H, CHCCl2); 3.99 (ddd, 1 H, J = 10.1, 5.9, 4.2,
CHCl); 4.27–4.40 (m , 2 H, CH2CH3). 13C NMR (CDCl3): 13.9, 25.0, 26.5, 28.2, 37.9, 54.7,
64.1, 166.6. IR (n eat): 3506 (w), 2940, 1761 (s), 1745, 1451, 1252, 1228 (s), 1023, 911, 732
(s). MS (EI), m/z (%): 272.2 (100), 274.1 (79) [M]+, 276.2 (67), 273.1 (14), 275.0 (12), 277.2
(4), 278.3 (3).
Ethyl 2,2-dichloro-3-[chloro(phenyl)methyl]-4-oxopentanoate (36). 1H NMR (CDCl3): (t, 3 H,
J = 7.1, CH2CH3); 2.57 (s, 3 H, CH3C(=O)-); 3.75 (q, J = 7.1, CH2CH3); 4.53 (d, 1 H, J = 9.6,
-CH); 5.45 (d, 1 H, J = 9.6, Ph CHCl); 7.33–7.39 (m , 4 H, Ar-H); 7.46–7.49 (m , 1 H, Ar-H).
13C NMR (CDCl3): 13.7, 34.1, 60.8, 64.5, 65.1, 81.9, 128.5, 129.3, 129.6, 137.9, 164.0, 202.2.
IR (n eat): 2986 (w), 1763, 1726 (m ), 1247, 1029, 907, 726 (s), 695. MS (EI), m/z (%): 336.0
(100), 338.0 (91) [M]+, 340.0 (29), 337.0 (17), 339.0 (14), 341.0 (5), 342.1 (4).
4,4-Dichloro-5-oxo-2-phenyltetrahydrofuran-3-yl methylacetate (38). 1H NMR (CDCl3): 1.86 (s,
3 H, CH3C(=O)-); 3.33–3.35 (m , 1 H, -CHCCl2-); 4.49 (dd, 1 H, J = 12.0, 6.2, acetate-CH2-);
4.56 (dd, 1 H, J = 12.0, 7.0, acetate-CH2-); 5.24 (d, 1 H, J = 9.8, Ph CHCl); 7.38–7.40 (m , 2 H,
Ar-H); 7.47–7.48 (m , 3 H, Ar-H). 13C NMR (CDCl3): 20.5, 31.2, 57.8, 59.6, 81.6, 127.3, 129.4,
130.4, 134.2, 166.8, 170.5. IR (n eat): 1799, 1742, 1225, 1184, 1044, 964, 770, 692. MS (EI),
m/z (%): 305 (30), 304 (7), 303 (44) [M]+, 235 (7), 209 (34), 208 (13), 207 (100), 179 (15).
1,3,3-Trichloro-4-ethoxy-4-oxobutyl benzoate (39). 1H NMR (CDCl3): 1.30 (t, 3 H, J = 7.1,
CH3CH2-OC(=O)-); 3.32 (dd, 1 H, J = 15.1, 3.3, -CH2CCl2-); 3.65 (dd, 1 H, J = 15.1, 8.7,
-CH2CCl2-); 4.23–4.29 (m , 2 H, CH3CH2OC(=O)-); 7.06 (dd, 1 H, J = 8.7, 3.3, CHCl);
7.49–7.52 (m , 2 H, Ar-H); 7.64–7.65 (m , 1 H, Ar-H); 8.07–8.08 (m , 2 H, Ar-H). 13C NMR
(CDCl3): 13.9, 52.1, 64.6, 77.3, 80.1, 128.5, 128.9, 130.4, 134.4, 163.7, 165.7. IR (n eat):
1742, 1243, 1052, 1082, 1023, 706, 684. MS (EI), m/z (%): 343 (13), 342 (7), 341 (42), 340
(11), 339 (53) [M]+, 307 (6), 306 (5), 305 (31), 304 (9), 303 (52), 105 (100). For C13H13Cl3O4
(339.6) calculated: 45.98% C, 3.86% H; foun d: 47.25% C, 4.11% H.
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1012
Mume, Munslow, Källström, Andersson:
Dimethyl 2-(2-chloro-2-phenylethyl)malonate (41). 1H NMR (CDCl3): 2.67 (m , 2 H, CHClCH2-);
3.70 (dd, 1 H, J = 8.0, 6.9, -CHC(=O)-); 3.78 (s, 3 H, CH3OCO-); 3.79 (s, 3 H, CH3OC(=O)-);
4.97 (dd, 1 H, J = 8.0, 6.8, Ph CHCl-); 7.57–7.69 (m , 5 H, Ar-H). 13C NMR (CDCl3): 39.0,
49.7, 53.0, 53.1, 61.1, 127.2, 128.9, 129.0, 140.7, 169.2, 169.4. IR (n eat): 1732, 1435, 1269,
1221, 1152, 697. MS (EI), m/z (%): 274 (4), 273 (26), 272 (15), 271 (100) [M]+, 238 (9), 236
(100), 235 (11), 232 (22).
The authors are grateful to The Swedish Research Council (VR) and the Wenner-Gren Foundation
(IJM) for financial support.
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