Categories: C-C Bond Formation > Arenes, Cyclic Compounds > Benzocycloalkenones

Synthesis of indanones

Related:

Recent Literature

Cyclization of electron-rich 2-alkyl-1-ethynylbenzene derivatives was catalyzed by TpRuPPh₃(CH₃CN)₂PF₆ in hot toluene to form 1-substituted-1H-indene and 1-indanone products. The cyclization mechanism involves a 1,5-hydrogen shift of an initial metal-vinylidene intermediate.
A. Odedra, S. Datta, R.-S. Liu, J. Org. Chem., 2007, 72, 3289-3292.

Indanones and 2-cyclopentenones have been successfully prepared in good to excellent yields by the palladium-catalyzed carbonylative cyclization of unsaturated aryl iodides and dienyl triflates, iodides, and bromides, respectively. The mechanism is discussed.
S. V. Gagnier, R. C. Larock, J. Am. Chem. Soc., 2003, 125, 4804-4807.

A nickel-catalyzed reductive cyclization of broad range of enones affords indanones in high enantiomeric induction. The versatility of this method is demonstrated in several short stereoselective syntheses of medically valuable (R)-tolterodine, (+)-indatraline, and (+)-multisianthol.
X. Qin, M. W. Y. Lee, J. S. Zhou, Org. Lett., 2019, 21, 5990-5994.

Enantioselective synthesis of chiral 3-aryl-1-indanones was achieved through a rhodium-catalyzed asymmetric intramolecular 1,4-addition of pinacolborane chalcone derivatives in the presence of MonoPhos as chiral ligand under relatively mild conditions. This reaction offers an easy access to various enantioenriched 3-aryl-1-indanone derivatives in high yields with excellent enantioselectivities.
Y.-N. Yu, M.-H. Xu, J. Org. Chem., 2013, 78, 2736-2741.

A catalytic amount of SbF₅ efficiently converted a mixture of phenylalkynes and aldehydes to indanone compounds in one pot in the presence of EtOH as an additive, and the reaction afforded the corresponding 2,3-disubstituted indanones as a single trans-isomer.
A. Saito, M. Umakoshi, N. Yagyu, Y. Hanzawa, Org. Lett., 2008, 10, 1783-1785.

The combination of In(OTf)₃ and benzoic acid synergistically promotes the coupling of alkynes and acetals to form 2,3-disubstituted indanones in excellent yield and diastereoselectivity via a tandem [2 + 2] cycloaddition and Nazarov reaction.
L. Zhu, Z.-G. Xi, J. Lv, S. Luo, Org. Lett., 2013, 15, 4496-4499.

A rhodium-catalyzed tandem carborhodium/cyclization and intramolecular proton shift pathway enables the synthesis of 2,3-substituted indanones in very good yields under very mild and sustainable conditions using water as the sole solvent without exogenous ligands. The reaction is compatible with a broad range of functional internal alkynes.
A. Zhu, Y. Sun, J. Lai, Z. Chen, X. Bu, Y.-N. Yue, M. Ma, F. Xue, J. Org. Chem., 2022, 87, 7884-7894.

A Ni-catalyzed formal exo-selective carboacylation of o-allylbenzamides with arylboronic acid pinacol esters provides 2-benzyl-2,3-dihydro-1H-inden-1-ones in good yields. The reaction is triggered by oxidative addition of an activated amide C-N bond to a Ni(0) catalyst and proceeds via alkene insertion into a Ni(II)-acyl bond.
J. A. Walker Jr., K. L. Vickerman, J. N. Humke, L. M. Stanley, J. Am. Chem. Soc., 2017, 139, 10228-10231.

An iridium-catalyzed alkylation of ketones with alcohols enables a one-step access to cyclic and linear ketones in high yields. A scale-up experiment for the synthesis of donepezil shows the excellent practicability of this protocol.
S. Wang, R. Miao, Y. Xia, Y. Wei, R. Luo, L. Ouyang, Synthesis, 2022, 54, 5253-5260.

The use of 2-(4,5-dihydroimidazol-2-yl)pyrimidine as ligand enables a Pd-catalyzed reaction of α,β-unsaturated esters with arylboronic acids to provide a wide range of 3,3-disubstituted indan-1-ones bearing a quaternary carbon in high yields. The reaction involves a tandem conjugate addition/1,4-Pd shift followed by a cyclization.
A. Gao, Y.-Y. Liu, H. Li, C.-H. Ding, X.-L. Hou, J. Org. Chem., 2017, 82, 9988-9994.

Enantioenriched CN-containing all-carbon quaternary stereocenters can be assembled by desymmetrizing cyclization of aryl/alkenyl halide-tethered malononitriles. The use of a silane reductant is crucial to the enantioselectivity and reactivity.
Z.-H. Chen, R.-Z. Sun, F. Yao, X.-D. Hu, L.-X. Xiang, H. Cong, W.-B. Liu, J. Am. Chem. Soc., 2022, 144, 4776-4782.

A palladium-catalyzed asymmetric C-C bond activation/carbonylation of cyclobutanones with CO provides chiral indanones bearing a quaternary carbon stereocenter in good yields with an excellent enantiomeric ratio and good functional group tolerance. Transformations of the products to chiral 3,4-dihydroquinolin-2(1H)-ones and 1H-indenes are also reported.
L. Chen, C. Shi, W. Li, B. Li, J. Zhu, A. Lin, H. Yao, Org. Lett., 2022, 24, 9157-9162.

A Rh(III)-catalyzed reaction of α-carbonyl sulfoxonium ylides with activated alkenes furnishes a variety of substituted indanone derivatives via a formal [4 + 1] cycloaddition. The reaction tolerates a broad range of functional groups.
Y. Kommagalla, S. Ando, N. Chatani, Org. Lett., 2020, 22, 1375-1379.

α-Ammonium acetophenones with an oxidizing C-N bond can serve as substrates for Rh(III)-catalyzed C-H activation under redox-neutral conditions. The coupling with α-diazo esters afforded benzocyclopentanones, and the coupling with unactivated alkenes such as styrenes and aliphatic olefins gave ortho-olefinated acetophenoes. In both systems the reactions proceeded with a broad scope, high efficiency, and functional group tolerance.
S. Yu, S. Liu, Y. Lan, B. Wan, X. Li, J. Am. Chem. Soc., 2015, 137, 1623-1631.

A facile and highly efficient copper-catalyzed intramolecular annulation of simple 2-ethynylbenzaldehyde derivatives provides 3-hydroxy-1-indanones under mild conditions in very good yields.
G. He, C. Wu, J. Zhou, Q. Yang, C. Zhang, Y. Zhou, H. Zhang, H. Liu, J. Org. Chem., 2018, 83, 13356-13362.

A highly enantioselective carboalkoxylation of alkynes catalyzed by cationic (DTBM-MeO-Biphep)gold(I) complexes enables the synthesis of various optically active β-alkoxyindanone and 3-methoxycyclopentenones derivatives in good yields with high enantioselectivities. The reaction proceeds through an enantioselective cyclization of intermediates containing vinylgold(I) and prochiral oxocarbenium moieties.
W. Zi, F. D. Toste, J. Am. Chem. Soc., 2013, 135, 12600-12601.

A migratory insertion of carbene followed by a Heck reaction enables the synthesis of 2-arylidene-3-aryl-1-indanones in excellent yields from very stable and easily accessible N-tosylhydrazones and 2′-iodochalcones through 5-exo-trig cyclization that delivers the products selectively with E configuration of the double bond. In situ synthesis of both 2′-iodochalcones and N-tosylhydrazones has also been demonstrated.
D. Arunprasath, P. Muthupandi, G. Sekar, Org. Lett., 2015, 17, 5448-5451.

A new palladium(0)-catalyzed three-component reaction of salicylic aldehyde triflates, ethylene glycol vinyl ether, and various secondary nucleophilic amines involving an initial internal Heck arylation, iminium ion formation, and subsequent tandem cyclization gives tertiary 3-aminoindan acetals.
A. Arefalk, M. Larhed, A. Hallberg, J. Org. Chem., 2005, 70, 938-942.

Related

The arylthiolated Au₂₅(F-Ph)₁₈^- nanocluster is synthesized and characterized. Ligands avoid distortion of the geometric structure, limit the Jahn-Teller effect, and protect the nanocluster from oxidization. The low energy gap (HOMO-LUMO) of the synthetic clusters enables photocatalytic oxidative functionalization reactions mediated by near-infrared light (850 nm).
S. Wang, L. Tang, B. Cai, Z. Yin, Y. Li, L. Xiong, X. Kang, J. Xuan, Y. Pei, M. Zhu, J. Am. Chem. Soc., 2022, 144, 3787-3792.

A chiral (1S,2S)-cyclohexanediamine backbone salen-zirconium(IV) complex as the catalyst enables a highly enantioselective α-hydroxylation of β-keto esters using cumene hydroperoxide (CHP) as the oxidant to provide chiral α-hydroxy β-keto esters in excellent yields and enantioselectivities. The zirconium catalyst is recyclable and the reaction can be performed in gram scale.
F. Yang, J. Zhao, X. Tang, G. Zhou, W. Song, Q. Meng, Org. Lett., 2017, 19, 448-451.