Asymmetric 1,4-addition of diethylzinc to cyclic enones catalyzed by Cu(I)-chiral sulfonamide-thiophosphoramide ligands and lithium salts

Article abstract of DOI:10.1002/adsc.200404321

The chiral sulfonamide-thiophosphoramide ligand L1, prepared from the reaction of (1R,2R)-(-)-1,2-cyclohexanediamine with diphenylthiophosphoryl chloride and p-toluenesulfonyl chloride, was used as a chiral ligand in Cu(MeCN)₄ClO₄-pr

Full text of DOI:10.1002/adsc.200404321

FULL PAPERS
Asymmetric 1,4-Addition of Diethylzinc to Cyclic Enones
Catalyzed by Cu(I)-Chiral Sulfonamide-Thiophosphoramide
Ligands and Lithium Salts
Min Shi,* Wen Zhang
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, 354 Fenglin Lu, Shanghai 200032, Peopleꢀs Republic of China
Fax: (þ86)-21-6416-6128, e-mail: mshi@pub.sioc.ac.cn
Received: October 20, 2004; Accepted: December 13, 2004
Supporting Information for this article is available on the WWW under http://asc.wiley-vch.de/home/.
Abstract: The chiral sulfonamide-thiophosphoramide series of chiral ligands represents a type of S,O-biden-
1
ligand L1, prepared from the reaction of (1R,2R)- tate ligands on the basis of H NMR, 31P NMR and
(ꢀ)-1,2-cyclohexanediamine with diphenylthiophos- 13C NMR spectroscopic investigations. The linear ef-
phoryl chloride and p-toluenesulfonyl chloride, was fect of ligand ee and product ee further revealed
used as a chiral ligand in Cu(MeCN)4ClO4-promoted that the active species is a monomeric Cu(I) complex
catalytic asymmetric addition of diethylzinc to cyclic bearing a single ligand.
enones using LiCl as an additive in which up to
90% ee can be realized under mild conditions within
0.5 h. This chiral ligand is stable and recoverable after Keywords: additive; asymmetric 1,4-addition; chiral
usual work-up and can be reused in the same catalytic sulfonamide-thiophosphoramide
ligand;
cyclic
asymmetric reaction. Moreover, it was found that this enones; diethylzinc; linear effect; lithium chloride
Introduction
amine or (1R,2R)-(þ)-1,2-diphenylethane-1,2-diamime
and the applications of these novel chiral ligands in
Conjugate addition reactions of organometallic re- asymmetric catalysis.[12]
agents to a,b-unsaturated carbonyl compounds consti-
Herein, we report the results of our novel chiral sulfon-
tute an important part of our standard repertoire of syn- amide-thiophosphoramide ligands derived from
thetic methods for C C bond formation.[1,2] Many chiral (1R,2R)-(ꢀ)-1,2-cyclohexanediamine and (1R,2R)-
ꢀ
catalysts have been developed to promote such transfor- (þ)-1,2-diphenylethane-1,2-diamime on the catalytic
mations.[2] Previously, the enantioselective conjugate enantioselective 1,4-conjugate addition of diethylzinc
addition of organometallic reagents (Grignard reagents, to cyclic enones. The method described here allows the
organolithium derivatives, and dialkylzinc species) has efficient, catalytic and moderate to high enantioselec-
been assisted more or less efficiently by chiral copper[3] tive functionalization of six- and seven-membered cyclic
and nickel catalysts.[4] A prominent position in this rap- enones within 0.5 h. In addition, the chiral ligands can be
idly expanding field is occupied by the copper-catalyzed easily recovered and reused in the same enantioselective
and chiral ligand-accelerated 1,4-addition of organozinc addition without loss of efficiency and enantioselectivi-
reagents originally introduced and rendered practical by ty.
Alexakis,[2g,5] Feringa,[6] Hoveyda,[7] Pfaltz[3 h,8] and oth-
ers.[3e,9] In particular, chiral phosphoramidites,[6c,10a, b]
phosphites,[8e,5d,10c–h] phosphines,[10i] aminophospha- Results and Discussion
nes,[10j–l] sulfonamides,[10m, n] peptide-based phosphi-
nes[7e] and diaminocarbene compounds[10o, p] were used The chiral sulfonamide-thiophosphoramide ligands L1 –
as ligands in the addition to cyclic enones with very L7 are readily synthesized by the reaction of (1R,2R)-
good enantioselectivities.
(ꢀ)-1-N-diphenylthiophosphorylcyclohexane-1,2-dia-
Recently, we are interested in the synthesis of a novel mine 1 and (1R,2R)-(þ)-1-N-diphenylthiophosphoryl-
type of air- and moisture-stable chiral thiophosphor- 1,2-diphenylethane-1,2-diamine 2[12d] with various sul-
amide ligand[11] based on a series of chiral binaphthale- fonyl chlorides. In Scheme 1, we illustrate the reaction
nediamine (BINAM), (1R,2R)-(ꢀ)-1,2-cyclohexanedi- procedures for the preparation of chiral ligands L1 –
Adv. Synth. Catal. 2005, 347, 535–540
DOI: 10.1002/adsc.200404321
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Table 1. The enantioselective 1,4-addition reaction of 2-cy-
clohexen-1-one with ZnEt2 catalyzed by copper salt and chir-
al ligand.[a]
Scheme 1. Synthesis of sulfonamide-thiophosphoramide li-
gands L1 – L7.
L7. In general, they can be synthesized by the reaction of
1 and 2 with the corresponding sulfonyl chlorides in the
presence of Et3N and a catalytic amount of DMAP in di-
chloromethane at 08C for 12 h in moderate yields.[13]
These obtained chiral ligands L1 – L7 are air- and mois-
ture-stable compounds under ambient conditions.
Using 2-cyclohexen-1-one 3 as the substrate and di-
ethylzinc as the Michael addition reagent, we examined
the 1,4-addition reaction in the presence of novel sulfon-
amide-thiophosphoramide ligands L1 – L7 with various
copper salts in a variety of solvents at different temper-
atures to develop the optimal reaction conditions. The
results are summarized in Table 1. As can be seen
from Table 1, L1 is the best chiral ligand for this enantio-
selective 1,4-addition reaction to give the product 4 with
[a]
Et2Zn was added after the addition of 2-cyclohexene-1-
one.
Isolated yield.
Determined by chiral GLC.
Determined by the sign of the specific rotation.
No reaction took place.
Not determined.
2-Cyclohexene-1-one was added after the addition of
[b]
[c]
[d]
[e]
[f]
[g]
Et2Zn.
[h]
Only 3 mol % of ligand was used.
Recovered L1 was used as ligand in this reaction.
[i]
62% ee in 97% yield at 258C within 0.5 h with the S con- found that, at 08C, the enantioselectivity of this addition
figuration (Table 1, entry 1). Chiral ligands L2 to L5 reaction was decreased to 60% ee for 1 h while at
gave the addition product 4 in lower ee as compared
ꢀ108C, the enantioselectivity was sharply decreased
with L1 under identical conditions (Table 1, entries 2 to 53% ee for 2 h and at ꢀ208C, the enantioselectivity
to 6). These results suggest that the substituent of aryl was further decreased to 45% ee for a prolonged reac-
group in the sulfonamide-thiophosphoramide ligands tion time (8 h), respectively (Table 1, entries 9 to 11).
plays an important role in chiral induction for the asym- From these results, the best condition for this reaction
metric 1,4-addition reaction. Using L6 or L7 synthesized is at room temperature (258C). Copper(I) salts such as
from (1R,2R)-(þ)-1,2-diphenylethane-1,2-diamine as a Cu(CH3CN)4ClO4 or Cu(CH3CN)4BF4 showed higher
chiral ligand, 4 was obtained in lower ee than with li- catalytic activity and chiral induction ability than
gands L1 to L5 under identical conditions (Table 1, en- CuOTf·1/2C6H6 or Cu(OTf)2 under the same conditions
tries 7 and 8). In addition, since this addition reaction (Table 1, entries 12 to 14). Solvent effects have been also
is sluggish in the absence of ligand, the enantioselective examined using L1 as a chiral ligand at 258C under oth-
conjugate addition by our catalytic ligand system is ap- erwise identical conditions. Although not routine, this
parently a ligand-accelerated process.[14] At lower tem- Cu(I)-catalyzed reactions can be carried out in solvents
perature, L1 is still active for this reaction but the adduct such as Et2O, toluene, dichloromethane or THF.[15] Et2O
4 was generally obtained in lower ee. For example, it was is the solvent of choice for this asymmetric addition re-
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1,4-Addition of Diethylzinc to Cyclic Enones
FULL PAPERS
Table 2. The enantioselective 1,4-addition reaction of 2-cy-
clohexen-1-one with ZnEt2 catalyzed by copper salt, chiral li-
gand and additives.[a]
action (Table 1, entries 15 to 17). When 2-cyclohexen-1-
one was added after the addition of Et2Zn compared
with the formal procedure, the ee was distinctly de-
creased to 23% (Table1, entry 18). If 3 mol % of ligand
was used in this reaction, the achieved ee of 4 was slight-
ly decreased to 53% (Table 1, entry 19). The best reac-
tion conditions are using Cu(CH3CN)4ClO4 (3 mol %)
as a catalyst precursor and L1 (6 mol %) as a chiral li-
gand in Et2O at room temperature. This asymmetric ad-
dition reaction is complete within 0.5 h under this reac-
tion conditions. Moreover, this chiral ligand is quite sta-
ble and can be recovered in 96% yield after usual work-
up. The recovered ligand L1 after usual work-up can be
reused in this reaction without loss of catalytic ability
and enantioselectivity (Table 1, entry 20).
The detailed mechanism of organocuprate addition to
a,b-unsaturated compounds has been studied before.[16]
A Cu(III) species has been suggested as the key inter-
mediate in the conjugate addition of cuprate to enone,[17]
which can be dissolved by admixture with LiX as an ad-
ditive.[18] In addition, in some asymmetric catalysis, the
addition of LiX can improve the enantiopurity of the re-
action product.[3k,8b,9b] Based on these results, we also ex-
amined the addition of some LiX in our reaction system
to improve the enantioselectivity. The results are indi-
cated in Table 2. As can be seen from these results, using
10 mol % of LiCl as the additive gives the best results
(Table 2, entries 2 to 8). LiCl only acts as an additive
in this reaction because no reaction occurred in the ab-
sence of Cu(MeCN)4ClO4 (Table 2, entry 1). The reac-
tion proceeded more quickly at ambient temperature
(258C) than at ꢀ208C to give the adduct in similar enan-
tioselectivities of 87% ee and 88% ee, respectively (Ta-
ble 2, entries 3 and 4). Solvent Et2O is better than iso-
propyl ether (i-PrOPr-i) to obtain higher enantioselec-
tivity (Table 2, entries 3 and 5). Other lithium salts
such as LiBr, LiClO4, LiOAc are not as effective as
LiCl in this reaction system (Table 2, entries 9 to 11).
LiCl is the best additive in this asymmetric catalytic sys-
tem (Table 2, entries 3, 9 to 11). Moreover, we found that
the ee of 4 can be slightly increased to 90% in the pres-
ence of 9 or 12 mol % of ligand L1 (Table 2, entries 12
and 13).
[a]
Additive was added to Cu(I) and ligand in Et2O and the
solution was stirred at room temperature for 1 h before
2-cyclohexen-1-one and Et2Zn were added.
Isolated yield.
Determined by chiral GLC.
[b]
[c]
[d]
Determined by the sign of the specific rotation.
No Cu(I) was used.
[e]
[f]
The reaction was carried out at ꢀ208C.
[g]
Diisopropyl ether was used as solvent.
[h]
9 mol % of ligand was used.
12 mol% of ligand was used.
[i]
Scheme 2.
dition product 5 was obtained in moderate yield with
Therefore, on the basis of the above-mentioned re- 47% ee in the presence of ligand L1 and for 2-cyclohept-
sults, it is very clear that the asymmetric conjugate addi- en-1-one, the corresponding 1,4-addition product 6 was
tion reaction can be carried out under mild conditions obtained in 95% yield with moderate ee (73% ee), re-
(room temperature) with high enantioselectivity in our spectively (Scheme 2).
catalytic system in the presence of LiCl which offers an-
other example of lithium salts as additives that increase
the enantioselectivity in asymmetric catalysis. Further- Conclusion
more, our chiral sulfonamide-thiophosphoramide li-
gand system is quite stable, easily available, recoverable We disclosed an efficient catalytic system for the enan-
and reusable in asymmetric catalysis.
tioselective 1,4-conjugate addition of diethylzinc to cy-
Under the optimized reaction conditions, the 1,4-ad- clic enones catalyzed by Cu(I) and novel chiral sulfon-
dition of diethylzinc to 2-cyclopenten-1-one and 2-cy- amide-thiophosphoramide ligands using LiCl as an ad-
clohepten-1-one have been also examined. It was found ditive, which are easily available, quite stable, recovera-
that for 2-cyclopenten-1-one, the corresponding 1,4-ad- ble and reusable in asymmetric catalysis. The catalytic
Adv. Synth. Catal. 2005, 347, 535–540
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537

Min Shi, Wen Zhang
FULL PAPERS
column chromatography on silica gel (eluent: petroleum ether/
ethyl acetate¼4/1) to afford L1 as a white solid.
system allows the efficient, catalytic and moderately to
high enantioselective functionalization of six- and sev-
en-membered cyclic enones, although it is not effective
for five-membered cyclic enones. Results of mechanistic
studies on this type of chiral S,O-bidentate ligands to the
copper center through 1H NMR, 31P NMR and 13C NMR
spectroscopic experiments and the linear effect of ligand
ee and product ee revealed that the active species is a
monomeric Cu(I) complex bearing a single ligand are
shown in the Supporting Information. Efforts are under-
way to extend the scope of these novel chiral ligands in
General Procedure for the Cu(I)-Catalyzed 1,4-
Conjugate Addition
A solution of Cu(CH3CN)4ClO4 (5.0 mg, 0.015 mmol) and L1
(15.0 mg, 0.03 mmol) in anhydrous Et2O (3 mL) was stirred
for 1 h at room temperature under an argon atmosphere.
Then, 2-cyclohexen-1-one (3; 48 mL, 0.5 mmol) was added
into the reaction mixture and the solution was stirred foranoth-
er 10 min. Et2Zn (1.0 mL, 1.0 mmol, 1.0 M solution in hexane)
was added dropwise within 30 seconds. The resulting mixture
was stirred at 258C for 0.5 h. The reaction was quenched by
the addition of 1 N hydrochloric acid aqueous solution
(4.0 mL). After extraction with ether (3ꢁ5.0 mL), the com-
bined organic layers were dried over anhydrous MgSO4. The
residue obtained upon removal of volatiles under vacuum
was purified by a flash column chromatography on silica gel
(eluent: pentane/ether¼30/1) to afford (S)-(ꢀ)-3-ethylcyclo-
hexanone (4) as a colorless oil; yield: 61 mg (97%). The ligand
L1 was recovered in 96% yield after chromatography.
ꢀ
other asymmetric C C bond forming transformations.
Experimental Section
General Remarks
All reactions were conducted in oven- (1358C) and flame-
dried glassware under an inert atmosphere of dry argon or ni-
trogen. Toluene was distilled from sodium metal; dichlorome-
thane was distilled from calcium hydride; diethyl ether, tetra-
hydrofuran and toluene were distilled from sodium metal/ben-
1
zophenone ketyl. H NMR, 13C NMR, and 31P NMR spectra
Supporting Information Available
1
were recorded at 300, 75 and 121 MHz, respectively. Mass spec-
tra were recorded by the EI method. All of the solid com-
pounds reported in this paper gave satisfactory C,H,N micro-
analyses. Commercially obtained reagents were used without
further purification. All reactions were monitored by TLC
with silica gel coated plates. P-Arus reagent [prepared by dis-
solving p-anisaldehyde (10 mL), acetic acid (7.5 mL), and con-
centrated H2SO4 (25 mL) in 95% ethanol (500 mL)] was used
for those substrates which do not have absorptions in UV re-
gion. Flash column chromatography was carried out using
200–300 mesh silica gel at increased pressure. Enantiomeric
ratios were determined by chiral GLC or HPLC analysis. The
absolute configuration was assigned by comparison the optical
rotation with reported data.[19] Racemic products were synthe-
sized according to the literature.[20] Melting points are uncor-
rected.
The linear effect study, mechanistic work on the basis of H
NMR, 31P NMR and 13C NMR spectroscopic measurements
of L1 in the absence or presence of Cu(I) salt, characterization
data for ligands L1 – L7, and analytical data of the conjugate
adducts (chiral GC) are available as Supporting Information
Acknowledgements
We thank the State Key Project of Basic Research (Project 973)
(No. G2000048007), Shanghai Municipal Committee of Science
and Technology, and the National Natural Science Foundation
of China for financial support (203900502, 20025206 and
20272069).
Typical Procedure: Synthesis of (1R,2R)-(þ)-N-
diphenylthiophosphoryl-N’-4-
methylbenzenesulfonamidecyclohexane-1,2-diamine
(L1)
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