Palladium(0)-Catalyzed Intermolecular Asymmetric Cascade Dearomatization Reaction of Indoles with Propargyl Carbonate

Lu Ding,[b] Run-Duo Gao,[a] and Shu-Li You

Fused indolenines are important structural cores of natural products and frequently appear in biologically active mole- cules (Figure 1).[1] Accordingly, extensive efforts have been de- voted to developing efficient methods for the construction of these scaffolds in a highly chemo- and enantioselective manner. In this regard, the recently emerging catalytic asymmetric dearomatization (CADA) reactions provide a large array of methods allowing for efficient access to fused indolenines from readily available indole derivatives.[2] Notably, transition- metal-catalyzed allylic dearomatization reactions of indoles have witnessed significant progresses in the past decade.[3,4,5] Recently, we realized the construction of fused indolenine skeletons in a cascade fashion.[6] In 2014, the Rawal group and we independently reported an intermolecular cascade dearo- matization reaction of indole-based bisnucleophiles with prop- argyl carbonate, leading to a series of spiroindolenines and spi- roindolines.  Moderate  enantioselectivity   (, 77 % ee)  was  ach- ieved for limited substrates (Scheme 1, reaction 1).[6a,7,8] Rawal and co-workers found that the indole N@H moiety could par- ticipate in the cyclization process when the nucleophilic side chain was decorated at the C2 position of the C3 methyl sub- stituted indole (Scheme 1, reaction 2).[7,9] Herein, we report a chemo- and enantioselective synthesis of  multisubstituted fused indolenines by Pd-catalyzed cascade dearomatization of indoles bearing a nucleophile at the  C2 position with  proparg- yl carbonate (Scheme 1, reaction 3).

 

We began our studies by examining the reaction of dimethyl 2-[(3-benzyl-1H-indol-2-yl)methyl]malonate (1 a) with methyl prop-2-yn-1-yl carbonate (2)  in  dimethylacetamide  (DMA)  in  the presence of a Pd catalyst derived from Pd2dba3. Firstly, sev- eral commercially available chiral phosphorus  ligands  were  tested (Scheme 2). The desired product 3a was obtained in moderate yields when Feringa ligand (S,S,Sa)-L1, BINAP (R)-L2, or Synphos (R)-L3 were used. However, the Pd complex de- rived from PHOX ligand (S)-L4 could hardly promote this reac- tion. It is worth noting that the reaction with L1 led to 3a in excellent   enantioselectivity   and   good    chemoselectivity  (94 % ee, 10:1 3 a/4 a). Encouraged by these results, phosphora- midite ligands L5-L9 were investigated, however, no better re- sults were obtained. Next, further optimization of the reaction conditions was carried out using L1 (Table 1). Reactions in vari- ous solvents, such as DMF, CH2Cl2, and THF, afforded compara- ble yields and enantioselectivity albeit with lower 3 a/4a ratios (entries 2–4), whereas MeOH and PhMe led to almost no reac- tion (entries 5–6). Further evaluation of the concentration  (entries 7–11)   of  1a  revealed  that  c = 0.2 mol L@1  was  optimal in terms  of  yield  (entry 8).  Pd2(4-OMe-dba)3  was  a  better  palladium source than Pd2dba3 and [Pd(allyl)Cl]2 (entries 12 and 13).[10] Furthermore, some additives were tested. To our delight, both yield and 3 a/4a ratio were improved remarkably when 4 a molecular sieves were used (82 % yield, 95 % ee, > 19:1 3 a/4 a, entry 15). Finally, the optimized reaction conditions were es- tablished as the following:  Pd2(4-OMe-dba)3  (2.5 mol%),  L1  (11 mol%), 4 a MS (100 mg) in DMA (1 mL) at 80 8C (entry 15). Notably, 4a could not be converted to 3a under the optimized
conditions, suggesting the formation of C@N is likely an irrever- sible process here.

 

With the optimized conditions in hands, we then explored the substrate scope of this reaction (Scheme 3). Firstly, sub- strates with different substituents on the benzyl group were examined. Both electron-donating (3b: 4-OMe; 3c: 4-Me; 3d: 3-Me) and electron-withdrawing (3e: 4-F; 3 f: 4-Cl) groups were found to be well tolerated. The corresponding products were obtained in good to excellent yields, with excellent chemo- and enantioselectivities (3 b–3 f, 78–82 % yields, 16.2 :1 to   > 19:1  3/4,   93–95 % ee).   When   the  benzyl  group  was changed to 2-thienyl or 2-naphthyl, the desired products could also be obtained with gratifying  re-  sults (3g: 79% yield, 15.6:1 3 g/4 g, 96% ee; 3h: 85% yield, > 19:1 3 h/4 h, 96% ee). Next, substrates with different substituents on the indole ring were investi- gated. The dearomatized products were afforded in excellent  yields,  chemo-  and  enantioselectivities when an electron-donating group (3i: 5-OMe, 3j: 5- Me)  was  installed  on  the  indole  ring  (3i:  84% yield,> 19:1  3 i/4 i,  96% ee ;  3j: 86%  yield,  > 19:1 3 j/4 j, 92 % ee).

 

Remarkably, when an electron-withdrawing group was introduced on the indole  ring  (3k: 5-F; 3l: 5-Cl; 3m: 5-Br; 3n: 6-F; 3o: 6-Cl), good to excel- lent yields, C/N ratios and excellent enantioselectivity were obtained (3 k–3o: 73–77 % yields, 4.2:1 to 11.7:1 3/4, 92–94 % ee). Notably, the formation of al- lylic amination products was more favorable when stronger electron-withdrawing group was introduced (from 5-F to 5-Br, 6-F to 6-Cl). These are probably due to the increased acidity of the indole N@H and more easily formed N nucleophiles caused by the electron-withdrawing substituent. When the elec- tron-withdrawing group on substrate 1 was  changed from methyl carbonate to ethyl carbonate, the desired product could also be obtained in good results (3p: 71% yield, 18.3 :1 3 p/4 p, 91% ee). Furthermore, when an aliphatic group was in- stalled at the C3 position, all substrates were well tolerated    (3 q–3v: 71–85 % yields, > 19:1 3/4 in all cases, 92–94 % ee). The structure and absolute configuration of product 3r were confirmed by an X-ray crystallographic analysis of an enantio- pure example (see the Supporting Information for details). Moreover, substrate 1w bearing a nucleophilic chain at the C3 position underwent the reaction smoothly, affording the bridged indoline 3w in 71 % yield and 96 % ee.

To demonstrate the utility of the current method, a gram-scale reaction and several transformations of the product were carried out (Scheme 4). The asymmetric cascade dearomatization reaction of 1a with 2 on a 3.0 mmol scale provided product 3a in 84 % yield and 95 % ee. Under Pd/C hydrogena- tion conditions, the exocyclic double bond  of product 3a was reduced and the benzyl group was also removed at the same time likely due to the driving force of aromatiza- tion, giving 5 in 92 % yield.  The  imine moiety in 3a could be reduced by NaBH3CN in acetic acid to afford 6 in 91 % yield. The relative configuration of 6 was determined by NOE analysis (for details, see the Sup- porting Information). Treatment of 6 with acetyl chloride and NaH produced 7 in quantitative yield. Finally, the double bond in 7 was oxidized with ozone to give ketone 8 in 64 % yield.

 

A proposed catalytic cycle is depicted in Scheme 5. The propargyl carbonate is acti- vated by Pd0 to give intermediate. Then, the nucleophilic side chain attacks intermediate to generate p-allyl palladium species. Upon the deprotonation of indole N@H, the C3 position of indole in III attacks p-allyl palla- dium moiety to deliver IV. Finally, product 3 is provided upon the liberation of palladium catalyst.

 

In conclusion, we have achieved an effi- cient palladium(0)-catalyzed intermolecular asymmetric cascade dearomatization reac- tion of indole derivatives with propargyl car- bonate. A series of multiply substituted fused indolenines were obtained in good to excellent yields, excellent chemo- and enan- tioselectivities. This method features mild reaction conditions and broad substrate scope. Further studies on the reaction mechanism are currently underway in our laboratory.

Acknowledgements
We thank the National Key R&D Program of China  (2016YFA0202900),  the  National  Basic Research Program of China (2015CB856600), NSFC (21572252, 21821002), Program of Shanghai Subject Chief Scientist (16XD1404300),    and    the    CAS    (XDB20000000,    QYZDY-SSW-SLH012) for generous financial support.

 

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Cevimeline hydrochloride Catalog No.:AA007ARD CAS No.:107220-28-0 MDL No.:MFCD01961045 MF:C10H18ClNOS MW:235.7740	trans-CevimelineHydrochloride Catalog No.:AA01DZFM CAS No.:107220-29-1 MDL No.:MFCD01961046 MF:C10H18ClNOS MW:235.7740
Ethyl 4-fluoro-2-nitrobenzoate Catalog No.:AA009NXM CAS No.:1072207-10-3 MDL No.:MFCD10566267 MF:C9H8FNO4 MW:213.1625	(S,S)-1,3-Bis(4-bromobenzyl)-2-chlorooctahydro-2-(2E)-crotyl-1H-1,3,2-benzodiazasilole Catalog No.:AA003CM4 CAS No.:1072220-37-1 MDL No.:MFCD18632567 MF:C24H29Br2ClN2Si MW:568.8470
2-(3-Hydroxyphenoxy)acetonitrile Catalog No.:AA00HAVG CAS No.:107223-69-8 MDL No.:MFCD11181964 MF:C8H7NO2 MW:149.1467	3-Methyl-1H-pyrazolo[3,4-c]pyridine Catalog No.:AA0082CB CAS No.:1072249-89-8 MDL No.:MFCD13191779 MF:C7H7N3 MW:133.1506
3,6-Dichloro-4,5-diethylpyridazine Catalog No.:AA007AR7 CAS No.:107228-53-5 MDL No.:MFCD17014878 MF:C8H10Cl2N2 MW:205.0844	3,6-Dichloro-4-ethylpyridazine Catalog No.:AA0037VU CAS No.:107228-54-6 MDL No.:MFCD17014877 MF:C6H6Cl2N2 MW:177.0312
3,6-Dichloro-4-cyclobutylpyridazine Catalog No.:AA00HAVH CAS No.:107228-57-9 MDL No.:MFCD25955161 MF:C8H8Cl2N2 MW:203.0685	6-(4-Methoxyphenyl)hexanoic acid Catalog No.:AA01AA0M CAS No.:107228-87-5 MDL No.:MFCD12172613 MF:C13H18O3 MW:222.2802
2-Pyridinamine, 3-[(3-chlorophenyl)methoxy]- Catalog No.:AA0082C5 CAS No.:107229-62-9 MDL No.:MFCD11195108 MF:C12H11ClN2O MW:234.6815	3-(cyclohexylmethoxy)pyridin-2-amine Catalog No.:AA01A8DY CAS No.:107229-69-6 MDL No.:MFCD10689932 MF:C12H18N2O MW:206.2841
Cevimeline Catalog No.:AA0082C4 CAS No.:107233-08-9 MDL No.:MFCD22577792 MF:C10H17NOS MW:199.3131	1-(2-Chloropropanoyl)indoline Catalog No.:AA009PNU CAS No.:107236-27-1 MDL No.:MFCD05263162 MF:C11H12ClNO MW:209.6721
Zirconium 1,4-dicarboxybenzene MOF (UiO-66) Catalog No.:AA01FOVW CAS No.:1072413-89-8 MDL No.:MFCD29037163 MF:C48H24O32Zr6 MW:1660.0290	5-Iodo-1-methyl-1h-indazole Catalog No.:AA007AR0 CAS No.:1072433-59-0 MDL No.:MFCD11977535 MF:C8H7IN2 MW:258.0590
methyl 4-(aminomethyl)-3-fluorobenzoate hydrochloride Catalog No.:AA01B6DP CAS No.:1072438-51-7 MDL No.:MFCD17171306 MF:C9H11ClFNO2 MW:219.6405	Methyl 2-(aminomethyl)pyridine-4-carboxylate, HCl Catalog No.:AA007T5E CAS No.:1072438-54-0 MDL No.:MFCD09878665 MF:C8H11ClN2O2 MW:202.6381
Methyl 6-(aminomethyl)nicotinate hydrochloride Catalog No.:AA008ZD7 CAS No.:1072438-56-2 MDL No.:MFCD11045450 MF:C8H11ClN2O2 MW:202.6381	Methyl 3-amino-5-bromopicolinate Catalog No.:AA008U25 CAS No.:1072448-08-8 MDL No.:MFCD17015929 MF:C7H7BrN2O2 MW:231.0467
2-Amino-2-(3-methylphenyl)acetic acid HCl Catalog No.:AA0082C0 CAS No.:1072449-62-7 MDL No.:MFCD06410554 MF:C9H12ClNO2 MW:201.6501	1-(Dimethylamino)-6-methylheptan-3-one Catalog No.:AA00HAVI CAS No.:107245-26-1 MDL No.:MFCD22683883 MF:C10H21NO MW:171.2798
monoMETHACRYLOXYPROPYL FUNCTIONAL POLYTRIFLUOROPROPYLMETHYLSILOXANE, symmetric, 50-70 cSt Catalog No.:AA01EIBU CAS No.:1072456-00-8 MDL No.: MF: MW:	1-Fmoc-4-(hydroxymethyl)piperidine Catalog No.:AA00995K CAS No.:1072502-03-4 MDL No.:MFCD02094489 MF:C21H23NO3 MW:337.4122
5-Nitro-2-((3-phenylpropyl)amino)benzoic acid Catalog No.:AA00385A CAS No.:107254-86-4 MDL No.:MFCD00153851 MF:C16H16N2O4 MW:300.3092	4-[[3-[2-(3-Chlorophenyl)ethyl]-2-pyridinyl]carbonyl]-1-piperidinecarboxylic Acid Catalog No.:AA008W2U CAS No.:107256-32-6 MDL No.:MFCD16251304 MF:C22H25ClN2O3 MW:400.8985
Pk14105 Catalog No.:AA003TQE CAS No.:107257-28-3 MDL No.:MFCD28969041 MF:C21H20FN3O3 MW:381.4002	3-(1-(Boc-amino)ethyl)-pyrrolidine Catalog No.:AA00HAVK CAS No.:107258-90-2 MDL No.:MFCD18073167 MF:C11H22N2O2 MW:214.3046
Ethyl 1-(boc-amino)cyclopropanecarboxylate Catalog No.:AA003PXD CAS No.:107259-05-2 MDL No.:MFCD11845623 MF:C11H19NO4 MW:229.2729	(1-Formyl-cyclopropyl)-carbamic acid tert-butyl ester Catalog No.:AA0037VS CAS No.:107259-06-3 MDL No.:MFCD10697899 MF:C9H15NO3 MW:185.2203
1-(1-Benzylpyrrolidin-3-yl)ethanamine Catalog No.:AA01A52R CAS No.:107259-16-5 MDL No.:MFCD22057269 MF:C13H20N2 MW:204.3113	4-Ethynyl-2-methylthiazole Catalog No.:AA008U6X CAS No.:107263-89-8 MDL No.:MFCD18207414 MF:C6H5NS MW:123.1756
1-Fluoropyridinium Triflate Catalog No.:AA003AZ0 CAS No.:107263-95-6 MDL No.:MFCD00013458 MF:C6H5F4NO3S MW:247.1674	1-Fluoro-2,4,6-trimethylpyridin-1-ium trifluoromethanesulfonate Catalog No.:AA003E92 CAS No.:107264-00-6 MDL No.:MFCD00067525 MF:C9H11F4NO3S MW:289.2472
1-Fluoropyridinium tetrafluoroborate Catalog No.:AA003E9M CAS No.:107264-09-5 MDL No.:MFCD00153176 MF:C5H5BF5N MW:184.9029	ethyl 2-(2-amino-3-cyano-4,5-dimethyl-1H-pyrrol-1-yl)acetate Catalog No.:AA00IYYI CAS No.:107267-88-9 MDL No.:MFCD04126142 MF:C11H15N3O2 MW:221.2557
3-((2-Methylallyl)oxy)aniline Catalog No.:AA0082BS CAS No.:107268-37-1 MDL No.:MFCD06801092 MF:C10H13NO MW:163.2163	IFLAB-BB F1703-0109 Catalog No.:AA008X8V CAS No.:107269-65-8 MDL No.:MFCD06623794 MF:C8H10ClN5 MW:211.6515