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Phosphine-Catalyzed Asymmetric Intermolecular Cross Vinylogous Rauhut-Currier Reactions of Vinyl Ketones with para-Quinone Methides Shenhuan Li, Yuanyuan Liu, Ben Huang, Tao Zhou, Hongmei Tao, Yuanjing Xiao, Lu Liu, and Junliang Zhang ACS Catal., Just Accepted Manuscript • Publication Date (Web): 22 Mar 2017 Downloaded from http://pubs.acs.org on March 23, 2017
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Phosphine-Catalyzed Asymmetric Intermolecular Cross Vinylogous Rauhut-Currier Reactions of Vinyl Ketones with para-Quinone Methides Shenhuan Li,‡ Yuanyuan Liu,‡ Ben Huang, Tao Zhou, Hongmei Tao, Yuanjing Xiao, Lu Liu* and Junliang Zhang* Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, 3663 North Zhongshan Road, Shanghai 200062, China. ABSTRACT: A chiral amide-phosphine bifunctional catalyst was developed and successfully applied to the asymmetric
intermolecular cross vinylogous Rauhut-Currier of alkyl vinyl ketones with para-quinone methides, offering excellent regioselectivity and stereoselectivity (up to >99% ee). This method provides a facile access to structurally diverse widely existed diarylmethine stereogenic centers with excellent enantioselectivity. Density functional theory (DFT) calculations have been carried out to understand the mechanism and enantioselectivity for this phosphinecatalyzed asymmetric transformation. KEYWORDS: Rauhut-Currier reaction, 1,6-conjugated addition, organocatalysis, chiral phosphines, para-quinone methides
The development of efficient approach to build carboncarbon bond enantioselectively is an important goal for organic chemists.1 Ideally, such a strategy requires finishing in atom economy, operational convenience, functional group/water/air tolerance, environmentally benign and easily scale-upable.2 In this field, asymmetric nucleophilic additions catalyzed by chiral phosphines with active olefins as nucleophiles have recently emerged as powerful methods to fulfill this ideal goal.3 Over the past decade, the enantioselective 1,2-addition of active olefins to aldehydes, ketones and imines, named Morita– Baylis–Hillman (MBH) reactions and aza-MBH reactions, have already been well established by Shi and others (Scheme 1a).4 However, in comparison to the related MBH reaction, the enantioselective intermolecular cross Rauhut-Currier (R-C) reactions,5-7 also known as vinylogous MBH reactions, have not been realized until 2011. Pioneering works were explored by Miller, Krische, Sasai and others.5,6 Later, Shi et al. have firstly developed an enantioselective intermolecular cross R-C reaction of maleimides with allenoates and penta-3,4-2-ones by quinidine-derived β-isocupreidine (β-ICD).7a Recently, Huang and we successfully realized the more challenging asymmetric intermolecular cross R-C reactions between vinyl ketones with 3-acyl acrylates using the bi- or multi-functional phosphine catalysts (Scheme 1b).7b-d Indeed, to the best of our knowledge, the asymmetric vinylogous R-C reaction (1,6addition) to extended conjugated systems remains unexplored so far. However, the vinylogous reactions may attract tremendous attention because they can naturally leave one more C-C
double bond in the product, providing a potential opportunity for the following transformations to construct the complex chiral molecules. During the course of our study on asymmetric R-C reaction, we wondered whether the scope of R-C reaction of two active olefins could be expanded to the vinylogous R-C reaction of vinyl ketones with extended conjugated πsystem such as para-quinone methides (p-QMs).8 If success, this strategy will provide a facile access to diarylmethine stereogenic centers, which are important motifs in natural products, bioactive and pharmaceutic molecules, such as (R)tolterodine, COP-840, (+)-Isolariciresinol and (-)-latifolin (Figure 1).9 Moreover, the realization of such a reaction would also prove the wide applicability of the nucleophilic phosphine catalysis in multiple π system, thus representing a significant advance in the area. However, this hypothesis poses considerable challenge due to the following: 1) in general, the acceptors in intermolecular R-C reaction were equipped two activators to improve the cross-reactivity, while there was only one activator in p-QMs; 2) the homo-R-C reaction of vinyl ketone, which is the inherent competitive side reaction over cross R-C reaction; and 3) despite a handful of enantioselective 1,6additions to p-QMs by interaction or activation of p-QMs with different catalysis modes have been successfully developed,10,11 none of them is carried out by the nucleophilic catalysis by activation of other components.
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ACS Catalysis Table 1. Optimization of reaction conditonsa
a) 1,2-addition (MBH reaction)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
XH R1
O
∗
X R
R1
R
1
P*
2
6
O
OH
5
R1
2
4
Well established
O-
*P
O
∗
O
R2
O
4
R1
3
2
1
O
R
1
O
R1
O
3
Unknown
R
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∗
R1
R
This work R2
O
c) 1,6-addition (Cross Vinylogous R-C reaction)
b) 1,4-addition (Cross R-C reaction)
Scheme 1. The phosphine catalysed enantioselective intermolecular 1,n-addition of vinyl ketones.
Entry
Cat.
Base
T [℃]
Yield [%]b
ee [%]c
1 2
(S, Rs)-4a (R, Rs)-4a
-
20 20
60 47
7 8
3
(S, Rs)-4b
-
20
33
12
4
(R, Rs)-4b
-
20
24
12
5
(S, Rs)-4c
-
20
58
20
6
(R, Rs)-4c
-
20
51
-3
7
(S, Rs)-W1
20
99
-14
8
(S)-4d
-
20
32
36
9
(S)-4e
-
20
trace
50
10
(S)-4f
-
20
NR
11
(S)-4g
-
20
52
82
12
(S)-4h
-
20
63
86
13
(S)-4i
-
20
62
87
14
(S)-4j
-
20
67
87
15
(S)-4k
-
20
38
88
16
(S)-4l
-
20
40
85
17
(S)-4m
-
20
60
90
Figure 1. Selected bioactive compounds containing a diarylmethine stereogenic center.
Figure 2. Screened chiral phosphines
With this hypothesis in mind, p-QM 1a and methyl vinyl ketone (MVK) 2a were selected as model substrates for reactions in toluene at 20 oC. Various chiral phosphine catalysts 4a-4n, easily synthesized in short steps12, were tested (Figure 2). To our delight, the reactions proceeds smoothly to deliver the desired 1,6-addition product 3aa albeit with in moderate yields with 3-20% ees under the catalysis of 4a-4c. Several commonly used H-bonding donors were equipped on amino group and tested (4d-4g). Wei-Phos W1, which have shown high performance in asymmetric intermolecular cross R-C reaction, displayed excellent activity but very low enantioselectivity in this transformation (Table 1, entry 7). Gratifyingly, the desired product could be obtained in 52% yield with 82% ee when the reaction was catalyzed by 4g containing 3,5bistrifluoromethyl benzoyl amide as the H-bonding donor (Table 1, entry 11). We then turned to examine the effect of alkyl substituent of the catalysts (4h-4n), the best result was obtained in 60% yield with 90% ee when the reaction was catalyzed by 4m with 3-methylpentan-3-yl as the bulkyl substituent (Table 1, entry 17). The reaction rate was dramatically accelerated without loss of enantioselectivity by the replacement of the toluene with trifluorotoluene as solvent (Table 1, entry 19). A slightly better result was obtained by adding 1 equivalent of K2HPO4 (Table 1, entry 20). Running the reaction at –20 oC intead of 20 oC further improve the enantioselectivity and the loading of 2a could be reduced to 2 equivalents (Table 1, entries 21 and 22). Other solvent, such as toluene and mesitylene, can improve slightly enantioselectivity, but lower the yield sharply (Table 1, entries 23 and 24).
18
(S)-4n
-
20
35
65
19d
(S)-4m
-
20
91
90
d
(S)-4m
K2HPO4
20
100
91
21d
(S)-4m
K2HPO4
-20
100
96
d,e
(S)-4m
K2HPO4
-20
100 (91)
96
e
(S)-4m
K2HPO4
-20
50
96
24e,f
(S)-4m
K2HPO4
-20
63
97
20 22
23 a
Unless otherwise noted, all reactions were carried out with 1a (0.1 mmol), 2a (0.5 mmol), 4 (10 mol%) and base (1 equiv) in toluene (1 mL) for 12-40 h. bYields were determined by 1HNMR using CH2Br2 as internal standard. Numbers in parathesis are isolated yield. cDetermined by HPLC. dF3CPh was used as the solvent. e2 equiv of 2a was used. fMesitylene was used as the solvent.
With the optimized conditions in hand, we then investigated the substrate scope of this asymmetric vinylogous Rauhut-Currier reaction. As shown in Table 2, the reactions of pQMs 1b-1j containing polysubstituents on the aryl ring with MVK 2a proceeded smoothly, affording 3ba-3ja in moderate to excellent yields with 90-99% ees. Those p-QMs with ortho-, meta- or para-substituted phenyl also could deliver the desired products in moderate to high yields with 87-93% ees (3ka3ra). To our delight, 2-naphthyl and 3-indolyl derived p-QMs are also suitable for this transformation, delivering the diarylmethine products 3sa-3ua with high ees. Other alkyl vinyl
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ketones (2b and 2c) also reacted with p-QMs 1 to afford the 1,6-addition products in good yields with excellent enantioselectivity (3bb-3ub). Furthermore, when the isopropyl (methyl) was installed on α- and α’-position in p-QM 1v (1w), the corresponding 3va (3wa) could be also obtained in 93% (68%) yield with 94% (82%) ee. Of note, the reaction of unsymmetric p-QM 1x gave the desired product 3xa in excellent yield and enantioselectivity. Unfortunately, the reaction of acrolein or aryl vinyl ketones with 1a did not occur in our catalytic system (For details, see supporting information). The absolute configuration of product (S)-3ua was determined by singlecrystal X-ray analysis, and all the other adducts were tentatively assigned.13
tion of 3ba could afford the desired products 5 in good yield with excellent stereoselectivity (> 20 : 1 dr, 99% ee, Scheme 2b). The carbonyl group of 3ba could undergo selective reduction to furnish the corresponding alcohol 6 in good yield without decreasing the enantioselectivity, but with low diastereoselectivity (Scheme 2c). The 2,6-di-tert-butyl groups were installed to stabilize the p-QMs but weakened the synthetic value of this transformation. To address this issue, an AlCl3mediated de-tert-butylation reaction was examined and optically active compounds 7 were produced in excellent yield and without loss of enantiopurity via the de-tert-butylation (Scheme 2d). Notably, the “one pot” vinylogous RC reaction/de-tert-butylation was also successful to give the 7ka in 67% overall yield with 92% ee. O
Table 2. Substrate scope
t-Bu
a
OH t-Bu (a) 5 mol% 4m 2a (2 equiv.)
MeO
3ba
1.3 g, 96% yield 99% ee
MeO OMe 1b 3 mmol scale
(b)
(c)
OH
OH t-Bu
t-Bu OH Me
MeO MeO
3ka, 92% ee X = 3-MeO (d) O 3ha, 90% ee X = 3,4-(Me O(CH 2)2O-) 3qa, 90% ee X X = 4-CN 7ka 96% yield, 92% ee 7ha 83% yield, 90% ee 7qa 90% yield, 89% ee
MeO 6, 95% yield dr = 1.1:1, 97%/99% ee
t-Bu
t-Bu
One pot 7ka 1k + 2a 67% yield, 92% ee
(a) KHPO 4, F3CPh, -20 oC, 4 d; (b) 4-CH 3C6H 4SH, DABCO, DCM, r.t., 48 h; MeO Me (c) CeCl3, NaBH 4, MeOH, 0 oC, MeO S(p-Tol) 4 h; MeO (d) 8-16 equiv AlCl3, benzene, 5, 64% yield r.t., 8-18 h. dr > 20:1, 99% ee O
Scheme 2. Gram scale-up and the transformation of product 3ba and 3ka.
a
Unless otherwise noted, all reactions were carried out with 1 (0.1 mmol), 2 (0.2 mmol), 4m (10 mol%) and K2HPO4 (1 equiv) in F3CPh (1 mL). b Yields of isolated products. c Determined by HPLC. dMesitylene was used instead of F3CPh. eToluene was used instead of F3CPh. fAt -40 oC. gAt room temperature. This phosphine-catalyzed enantioselective intermolecular cross vinylogous Rauhut-Currier reaction is easy to scale-up. A gram-scale reaction of 1.15 g of 1b (3 mmol) and 2a (6 mmol) was carried out with a lower catalyst loading (5 mol %), furnishing 1.3 g of 3ba in 95% isolated yield without any loss of selectivity and efficiency (99% ee, Scheme 2a). Additionally, several further synthetic transformations of the products (3ba and 3ka) were also conducted. The sulfur-Michael addi-
DFT calculations have been undertaken (see SI for details) to understand the reaction mechanism and enantioselectivity. A plausible pathway for the reaction of p-QM 1k with MVK 2a catalyzed by 4h was shown in Scheme 3. Firstly, the capture of MVK via H-bonding of amide on catalyst affords a stable complex B. Such process is highly exoenergtic by -11.7 kcal/mol. Then B undergoes P-Michael addition, forming the key zwitterion specie C, which is stabilized by the intramolecular hydrogen bonding between the NH moiety of amide and the oxygen atom of carbonyl group. The C−H···F bonding between CF3 of C and p-QM 1r plays a crucial role in the formation of the stable complex D. The Re-face attack of D leads to the generation of an intermediate E by overcoming a small barrier of 8.6 kcal/mol via TS-D. Finally, the intermediate E is readily converted into product (R)-3ra through proton transfer and substrate exchange. In this transformation, the calculated difference in the thermal Enthalpies of the transition state (TS-D/D’) of attacking stage for the Re-face and Si-face pathways is 3.2 kcal/mol, which agrees to the experimentally observed ee values in the catalytic reactions. In the Re-face pathway, p-QM 1k finds configuration to right fit in the catalyst hole and interacts weakly by C−H···F bonding with both CF3 of the catalyst 4h, which causes the stabilization of TS-D. Therefore, C−H···F bonding and π−π stacking between p-QM 1r and enol intermediate from the phosphine and MVK assist the discrimination of the two TSs, leading to very high stereoselectivity. The role of the K2HPO4 may act as proton shuttle to accelerate the regeneration of the catalyst from the intermediate E (see Supporting Information for more details).
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ACKNOWLEDGMENT We are grateful to 973 Program (2015CB856600) and the National Natural Science Foundation of China (21425205, 21572065, 21502052, 21672067) for financial supports and Changjiang Scholars and Innovative Research Team in University (PCSIRT) for financial supports. The computation is performed in the Supercomputer Center of ECNU.
REFERENCES
Scheme 3. Proposed enantioselective pathway with thermal Enthalpies. In summary, we have developed a phosphine-catalyzed asymmetric intermolecular cross vinylogous Rauhut-Currier reaction of alkyl vinyl ketones to para-quinone methides. This method provides a facile access to structurally diverse diarylmethines with excellent enantioselelctivity. To the best of our knowledge, this is the first 1,6-addition to multiply π acceptor via nucleophilic catalysis. The salient features of this transformation includes broad scope of substrates, mild conditions, high enantioselectivity, ease of operation, easy scale-up to gram-scale and diverse convenient transformations of the products. In addition, the reaction mechanism was investigated by DFT computations, which agreed well to the experimentally observed enantioselectivity in the catalytic reactions. This work will promote not only the design of novel chiral phosphine catalysts, but also the development of methodologies on the utilization of multiple vinylogous enones in asymmetric catalysis.
ASSOCIATED CONTENT AUTHOR INFORMATION Corresponding Author
[email protected];
[email protected] Author Contributions ‡These authors contributed equally.
Notes The authors declare no competing financial interest.
Supporting Information Experimental procedures and characterization data. This material is available free of charge via the Internet at http://pubs.acs.org.
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