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A Regio- and Enantioselective Cuh-catalyzed Ketone Allylation With Terminal Allenes Review

Written By Sunday, April 17, 2022 Add Comment Edit

Abstract

Catalytic asymmetric conjugate allylation of unsaturated carbonyl compounds is commonly difficult to attain, as 1,2-addition proceeds dominantly and high asymmetric induction is a challenging task. Herein, we disclose a copper(I)-NHC complex catalyzed asymmetric 1,6-conjugate allylation of 2,two-dimethyl-6-alkenyl-4H-1,3-dioxin-4-ones. The phenolic hydroxyl group in NHC ligands is plant to be pivotal to obtain the desired products. Both aryl group and alkyl group at δ-position are well tolerated with the corresponding products generated in moderate to loftier yields and loftier enantioselectivity. Moreover, both 2-substituted and 3-substituted allylboronates serve equally acceptable allylation reagents. At last, the synthetic utility of the products is demonstrated in several transformations by means of the versatile terminal olefin and dioxinone groups.

Introduction

Catalytic asymmetric conjugate addition of various metal reagents to unsaturated compounds is identified equally i of the about of import tools in the construction of carbon-carbon bonds in organic synthesisane,two,3. Among the various carbon-based metal reagents, allyl metal reagents exhibit advantages over other alkyl metal reagents as the olefin moiety is more than synthetically versatile. Not-enantioselective methods based on different allyl metal (such as, Si, B, Zn, and Sn) species take been disclosed in the by several decades4. Nonetheless, the catalytic disproportionate conjugate addition with allyl metal reagents is all the same in its infancy equally such a reaction is not easy to achieve due to the competitive 1,2-addition and the difficulty in the disproportionate consecration.

Indeed, catalytic asymmetric allylation of aldehyde, ketone, and imine receives significant enquiry efforts from the chemical community, which leads to the identification of efficient catalytic systems based on Cu5,vi,7,8,9,10,11,12,13,14,fifteen,sixteen, Zn17,18, Ag19,20,21,22, and In23,24. The proposed vi-membered band transition state formed by the coordination of the allyl metal species to carbonyl group allows excellent asymmetric induction. Especially, copper(I)-catalysts serve as powerful weapons to enable the highly enantioselective allylation of carbonyl groups and imines5,six,vii,8,9,10,11,12,13,xiv,xv,16. However, the analogousness of the highly nucleophilic allylcopper(I) species to carbonyl grouping set up upwards an obstruction on the conjugate allylation. For case, in the presence of ten mol % copper(I)-(R)-BINAP, two equiv allylboronate, and one equiv LiO t Bu, the allylation of α,β-unsaturated ester produced 3rd alcohol just and the 1,iv-conjugate allylation production was non obtained (Fig. 1a). Moreover, without the help of the vi-membered ring transition country, at that place is a concern about the enantioselectivity in the conjugate allylation.

Fig. i: Prior arts in catalytic asymmetric cohabit allylation and our work.
figure 1

a Failed copper(I)-catalyzed disproportionate conjugate allylation. b Reported catalytic asymmetric conjugate allylation. c This work: copper(I)-catalyzed asymmetric conjugate 1,6-allylation.

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Several research grouping made their contributions in the challenging catalytic asymmetric cohabit allylation (Fig. 1b)25,26,27,28,29,30,31,32,33. Snapper reported a Cu(Two)-BOX-catalyzed asymmetric cohabit allylation of unsaturated cyclic β-keto-esters with allylsilane25. In 2007, Morken and co-workers disclosed an impressive Ni-catalyzed regioselective cohabit allylation of α,β-α′,β′-di-unsaturated ketones26. Later, the Morken group uncovered 2 efficient methods to carry out the catalytic asymmetric version in splendid command of the regioselectivity with either a palladium catalyst or a nickel goad27,28. The Hoveyda grouping achieved a three-component reaction of one,3-butadiene, BiiPinii and alkylidenemalonates in loftier yields with excellent enantioselectivity29. However, aliphatic substituents were non well tolerated at the β-position. The same group also succeeded in the catalytic enantioselective 1,6-cohabit allylation of α,β,γ,δ-unsaturated diesters with BtwoPivot2 and allenes30,31. In 2011, the Feng group achieved an asymmetric conjugate allylation of activated unsaturated lactones with a bimetallic catalytic organization32. In 2019, the same group reported a formal catalytic disproportionate 1,4-allylation of β,γ-unsaturated α-ketoesters4. In fact, the formal conjugate allylation was enabled by the allylation of the ketone group and the following oxy-Cope rearrangement. Unfortunately, alkyl was not well tolerated at the γ-position every bit merely moderate enantioselectivity was observed. Moreover, Shibasaki and Kumagai uncovered a catalytic asymmetric cohabit allylation of α,β-unsaturated thioamides with allyl cyanide under proton-transfer weather condition33. In view of the above achievements, we are interested in developing a catalytic disproportionate conjugate 1,half dozen-allylation with more general substrate structure and broader substrate scope.

Copper(I)-catalyzed asymmetric 1,6-add-on with alkyl metal reagents (such as organozinc reagent and Grignard reagent) has been reported equally a powerful tool to regio-selectively construct carbon-carbon bonds34,35,36,37,38,39,forty,41,42,43,44,45,46. Herein, nosotros disclose an asymmetric 1,6-conjugate allylation of 2,2-dimethyl-6-alkenyl-ivH-1,3-dioxin-four-i with a copper(I)-NHC catalyst (Fig. 1c). The 2,2-dimethyl-fourH-ane,three-dioxin-4-i moiety is an equivalent of the synthetically versatile β-keto-ester group and the product containing both an allyl group and a dioxinone group allows further structure elaboration. Furthermore, in view of the beefy steric hindrance around the carbonyl grouping and the relative stability of the lactone moiety, information technology is envisioned that the highly nucleophilic allylcopper(I) species would not touch the carbonyl group in the dioxinone and thus would set on the less hindered cohabit carbon-carbon double bond to requite the desired 1,6-allylation.

Results

Conditions optimization

First of all, the catalytic disproportionate conjugate allylation of (E)-two,ii-dimethyl-6-(4-phenylbut-1-en-1-yl)-fourH-i,3-dioxin-four-one (1a) with bench-stable allylboronate 2 was studied in the presence of 5 mol % Cu(CHthreeCN)4PF6, 6 mol % (R)-BINAP, and 1 equiv LiO t Bu (Tabular array 1, entry 1). The conjugate allylation proceeded smoothly to afford production 3a in 25% yield with 9% ee. Then, screening of commercially available bisphosphine ligands was performed and proved to exist fruitless (entries 2-vi). Particularly, (R,R)-Ph-BPE, the previously reported best ligand for the copper(I)-catalyzed allylation of ketonesnine,eleven,xiii, only led to 38% ee (entry 3). Moreover, ferrocene-embedded bisphosphine ligands, such as (R,R P )-TANIAPHOS and (R)-(South)-JOSIPHOS, were non constructive either (entries v-6). Obviously, copper(I)-bisphosphine catalyst did not conform this conjugate 1,half-dozen-allylation.

Tabular array 1 Optimization of reaction weather conditiona.

Total size table

Then, we turned our attention to NHC ligands (Table ane). Five NHC ligands were synthesized according to literature methods47,48,49. NHC-L1 was completely ineffective to go disproportionate induction in this 1,half-dozen-conjugate allylation (entry 7). A minor but promising 8% ee was obtained in the reaction with NHC-L2 (entry viii). Since phenol-containing NHCs (including NHC-L3-L5) were identified as powerful ligands in some copper(I)-catalyzed enantioselective reactions past the Sawamura Group49,fifty,51,52, NHC-L3 was tried in our reaction, which provided 3a in 10% yield with 64% ee (entry ix). To our joy, ninety% ee was observed with NHC-L4 (entry 10). Even so, decreased enantioselectivity (82% ee) was obtained in the reaction with bulkier NHC-L5 (entry 11). The yield was increased to 50% by using 10 mol % copper(I) table salt and 12 mol % NHC-L4 (entry 12). By increasing the amount of LiO t Bu from 1 equiv to 2 equiv, the yield was further increased to 85% with 89% ee (entry 13). Performing the reaction at −20 °C resulted in increased enantioselectivity (95% ee) but with decreased yield (53%) (entry 14). The yield was enhanced to 84% yield with 94% ee at −twenty °C by using 3 equiv allylboronate and 3 equiv LiO t Bu (entry 15).

Substrate scope

With the optimized reaction conditions in hand, the substrate telescopic of (E)-2,2-dimethyl-6-alkyl-ivH-ane,3-dioxin-4-ones was studied (Fig. two). Linear alkyls, including ethyl (3b), due north propyl (3c), and n heptyl (3d), were well tolerated and the corresponding products were isolated in expert yields with high enantioselectivity. β-Branched alkyl ( i butyl) (3e) was also accepted at the δ-position. The substrates bearing a α-branched alkyl with bigger steric hindrance (3f and 3g), afforded the allylated products in moderate yields and slightly decreased enantioselectivity. Then, substrates with an alkyl containing a functional group, such every bit benzyl (3a), terminal alkene (3h), internal alkyne (3i), alkyl chloride (3j), ester (3k), TBS-ether (3l), and Northward-Boc (3n) were examined. To our joy, the products were obtained in moderate to high yields and high enantioselectivity. Notably, alkyl chloride and ester group were non touched by the nucleophilic allylcopper-NHC species, demonstrating that allylcopper-NHC species was less nucleophilic than allylcopper-bisphosphine species. Unfortunately, the substrate containing a gratis alcohol (3m) was not tolerated. A substrate with a preexisting chiral center (3o) was likewise studied. The allylated product was generated in 72% yield with 91% de, indicating that the disproportionate consecration was mainly controlled by the copper(I) goad. It should exist noted that in some cases, the reaction temperature was increased to go proficient yields.

Fig. 2: Substrate scope of (East)-2,2-dimethyl-half dozen-alkyl-4H-ane,3-dioxin-4-ones in the ane,6-conjugate allylationa.
figure 2

Various aliphatic substituents at δ-position are studied.

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The reaction conditions were practical to the catalytic asymmetric allylation of (Due east)-two,ii-dimethyl-6-aryl-ivH-1,iii-dioxin-4-ones with 4 equiv allylboronate (2) as 3 equiv ii generally resulted in inferior yields (Fig. iii). The reaction was not very sensitive to the position of a substituent on the phenyl ring. As the allylated products containing a para-substituent, ortho-substituent, or meta-substituent were isolated in moderate to loftier yields with uniformly loftier enantioselectivity (5a–5o). It was noted that substrates with electron-withdrawing groups led to lower yields merely with maintained enantioselectivity (5d–5f, vm, and 5o). Moreover, substrates with electron-donating groups served as competent substrates as the corresponding products were furnished in adept yields with high enantioselectivity (5b–5c, 5h–5i, and 5k–5l).

Fig. 3: Substrate telescopic of (E)-ii,2-dimethyl-vi-aryl-4H-ane,3-dioxin-four-ones in the one,vi-conjugate allylationa.
figure 3

Various aromatic substituents at δ-position are studied.

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The phenyl group at δ-position was successfully changed to 2-naphthyl group without affecting both yield and enantioselectivity significantly (5p). Moreover, several heteroaryl groups, including 3-pyridyl (5q), ii-furanyl (5r), 2-benzofuranyl (5s), 3-benzothienyl (5t), and three-N-Boc-indolyl (5u), were successfully tolerated at the δ-position. The corresponding products were furnished in moderate yields with uniformly loftier enantioselectivity. It should be pointed out that the reaction temperature varied in order to get good yields. The accented configuration of 5a was determined to be S by its transformation to a known chemical compound (for the details, see SI). The absolute configurations of other products (3 and 5) were deduced by analogy.

Then, the one,half-dozen-cohabit allylation with ii-substituted allylboronates (six–8) was investigated as shown in Fig. 4. Several aryl groups, including phenyl, 2-F-phenyl, and 3-methyl-phenyl, were well tolerated at the δ-position in the reaction with 6. The corresponding products (9a–9c) were obtained in 57%-63% yield with 93%-97% ee. An alkyl group, such every bit 2-phenyl-ethyl, was also acceptable at the δ-position (9d). 2-Methyl group in allylboronate 6 was successfully extended to 2-benzyl and n hexyl without eroding both yields and enantioselectivity (10–11). Moreover, the reactions of both iii-methyl-(E)-allylboronate (12a) and 3-methyl-(Z)-allylboronate (12b) were studied as shown in Fig. 5. The diastereoselective allylation of 4j and 12a proceeded smoothly to afford 13 in moderate yield with moderate diastereoselectivity and excellent enantioselectivity. Surprisingly, the reaction with 12b as well furnished xiii as the production in decreased yield and slightly decreased enantioselectivity. At this stage, it is difficult to understand such experimental results. All the same, information technology is speculated that the add-on of the (Z)-allylcopper(I) is kinetically unfavored and the isomerization of (Z)-allylcopper(I) species to (E)-allylcopper(I) might occur through one,3-translocation in the present reaction conditions53. The absolute configurations of 9, x, and 11 were deduced analogically based on the stereochemical structure of 5a. Moreover, the absolute configurations of the two stereogenic carbon centers in thirteen were determined past its transformation (For the details, see SI). In addition, the present catalytic arrangement was extended to the asymmetric additions with PhMgBr and EtMgBr. Withal, simply racemic products were obtained54.

Fig. 4: Preliminary investigation of i,six-cohabit allylation with two-substituted allylboronates (6–viii)a.
figure 4

Both effluvious and aliphatic substituents at δ-position are tried.

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Fig. 5: Diastereoselective one,6-conjugate allylation.
figure 5

a The i.6-conjugate allylation with (E)-allylBPin. b The 1,vi-cohabit allylation with (Z)-allylBPin.

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Demonstration of the importance of the phenol group in NHC ligands

Several ligand variants of NHC-L4 were prepared to investigate the importance of the naphthol group (Fig. half dozen). The allylation with NHC-L6 containing a protected naphthol group did not beget the product 3a at all. Moreover, the reaction using NHC-L7 without the naphthol moiety was fruitless. Interestingly, NHC-L8 bearing a naphthol group and a protected naphthol group was plant as a good ligand every bit product 3a was generated in 32% yield with 85% ee. These control experiments demonstrate that a gratuitous naphthol moiety is indispensable for this reaction to keep. Furthermore, the steric hindrances on the both aryls are responsible for the disproportionate induction. Our finding of the essentiality of the free phenol or naphthol in this type of NHC ligands in asymmetric catalysis with copper(I) is in accordance with Sawamura's original findings49,50,51,52.

Fig. 6: Control experiments with unlike NHC-ligands.
figure 6

The importance of the presence of a phenol grouping in NHC-ligands is demonstrated.

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Transformation

At terminal, transformations of 5d were performed as described in Fig. 7. An Ir-catalyzed hydroborylation of final olefin moiety in 5d afforded boronate 14 in 62% yield55. The olefin-metathesis betwixt 5d and 4-methylstyrene with x mol % Hoveyda-Grubbs goad 2nd generation produced (E)-olefin 15 in 71% yield at forty °C (>20/1 (Due east) form/(Z) form ratio). Removal of the propylidene grouping in 5d was achieved in MeOH to give β-keto-ester xvi in 75% yield. And so, a synthetic sequence, including the reduction of ketone unit of measurement, the germination of a mesylate, and the subsequent emptying furnished α,β-unsaturated ester 17 in sixty% total yield. It should exist noted that 16 serves as a formal 1,iv-cohabit allylation product of α,β-unsaturated ketone and 17 serves as a formal i,6-cohabit allylation product of α,β,γ,δ-unsaturated ester, which are difficult to access by known methods. Moreover, the training of pyrazole 18 was achieved by means of the β-keto-ester motif through a reported procedure56.

Fig. vii: Transformations of product 5d.
figure 7

a Ir-catalyzed hydroboration. [Ir(COD)Cl]2 (v mol %), dppm (PhiiPCH2PPh2) (ten mol %), HBPin (2 equiv), CH2Clii, rt. b Olefin Metathesis. Hoveyda-Grubbs II goad (10 mol %), 4-methylstyrene (ii equiv), CH2Clii, xl °C. c Transformation to β-keto-ester. MeOH, KiiCOiii, rt. d Transformation to α,β-unsaturated ester. (ane) NaBHiv, MeOH, 0 °C; (2) MsCl, EtthreeNorthward, CH2Cl2, 0 °C to rt. east Transformation to pyrazole. NH2NH2•HCl (2 equiv), MeOH, reflux.

Full size paradigm

Give-and-take

In summary, a catalytic asymmetric one,6-conjugate allylation was achieved in moderate to high yields with loftier enantioselectivity. NHC ligands containing a phenolic hydroxyl grouping were establish to be indispensable to enable this reaction. Both 2,2-dimethyl-6-alkenyl-4H-one,iii-dioxin-4-one and allylboronate enjoyed broad substrate scopes. Several functional groups, especially alkyl halide and ester, were well tolerated in this reaction. The allyl grouping in the product allowed facile both hydroboration and olefin metathesis to give synthetically useful products. Moreover, the versatile dioxinone group was easily transformed to β-keto-ester moiety and α,β-unsaturated ester moiety, which generated a formal i,4-conjugate allylation production of α,β-unsaturated ketone and a formal ane,vi-conjugate allylation production of α,β,γ,δ-unsaturated ester. Detailed investigations of the mechanism are currently undertaken in our laboratory.

Methods

A general procedure for the catalytic asymmetric 1,6-conjugate allylation

A dried 25 ml Schlenk tube equipped with a magnetic stirring bar was charged with CuPF6(CHiiiCN)four (3.7 mg, 0.01 mmol, 0.i equiv), NHC-L4 (6.2 mg, 0.012 mmol, 0.12 equiv) and LiO t Bu (24.0 mg, 0.3 mmol, 3 equiv) in a glove box under Ar temper. Anhydrous THF (1 ml, 0.1 Thou) was added to the tube via a syringe. The resulting mixture was stirred nether room temperature for 7 min. Then 1 (0.1 mmol, 1 equiv) was added to the reaction mixture. It was cooled down to the stated temperature before adding 2 (50.4 mg, 0.three mmol, 3 equiv) by a syringe. This mixture was stirred for 12–36 h at that temperature. Then the reaction was quenched by calculation silica gel and the mixture was purified by flash silica gel column chromatography to give product 3.

Data availability

The data supporting the findings of this study are available inside the article and its Supplementary Information file. Any further relevant data are available from the authors on request.

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Acknowledgements

We gratefully acknowledge the financial support from the National Natural Scientific discipline Foundation of Communist china (No. 21672235, No. 21871287, and No. 21922114), the Program of Shanghai Academic/Technology Inquiry Leader (20XD1403600), the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB20000000), CAS Fundamental Laboratory of Synthetic Chemistry of Natural Substances and Shanghai Institute of Organic Chemistry.

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Affiliations

  1. The Enquiry Eye of Chiral Drugs, Innovation Inquiry Found of Traditional Chinese Medicine and China-Thailand Articulation Research Institute of Natural Medicine, Shanghai University of Traditional Chinese Medicine, 1200 Cailun Route, 201203, Shanghai, Communist china

    Chang-Yun Shi, Ping Tian & Liang Yin

  2. CAS Cardinal Laboratory of Synthetic Chemistry of Natural Substances, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, 200032, Shanghai, Prc

    Chang-Yun Shi, Zhi-Zhou Pan & Liang Yin

Contributions

L.Y. and P.T. conceived and designed the study. C.Y.Due south. and Z.Z.P. performed the synthetic experiments and analyzed data for all new compounds. L.Y. wrote the newspaper.

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Correspondence to Ping Tian or Liang Yin.

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Shi, CY., Pan, ZZ., Tian, P. et al. Copper(I)-catalyzed asymmetric 1,half-dozen-conjugate allylation. Nat Commun eleven, 5480 (2020). https://doi.org/ten.1038/s41467-020-19293-9

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