Catalytic reduction reactions using isopropanol(IPA) as a transfer hydrogenating agent are gaining significant attention due to the low cost and large-scale production of IPA. Traditional methods for carbon-carbon(C — C) bond construction often rely on expensive and scarce transition metal catalysts, raising concerns about sustainability and environmental impact. To address these challenges, we develop a bifunctional photocatalyst, phloroglucinol carbon quantum dot(PG-CQD). It facilitates catalytic transfer hydrogenation(CTH) with IPA as the hydrogen donor. PG-CQDs exhibit both dehydrogenation and reduction activities, enabling the formation of vicinal diols under mild conditions with visible light irradiation. We propose a CTH mechanism that has been successfully validated through experiments. The catalytic system demonstrates remarkable versatility, enabling the synthesis of various vicinal diols from diverse α-keto ester substrates with good or excellent yields. These findings offer a sustainable synthetic strategy that aligns with green chemistry principles and establish a promising pathway for the development of environmentally benign and energy-efficient organic transformations.
| [1] |
SHI Y, XU X F, CHEN X F, et al. Synthesis of cyclopentenes and cyclohexenes via cobalt(Ⅱ)-catalyzed oxidative cyclization[J]. Journal of Organic Chemistry, 2021, 86(21):15335-15344.
|
| [2] |
NICOLAOU K C, BULGER P G, SARLAH D. Palladium-catalyzed cross-coupling reactions in total synthesis[J]. Angewandte Chemie International Edition, 2005, 44(29):4442-4489.
|
| [3] |
HU Y J, GU C C, WANG X F, et al. Asymmetric total synthesis of taxol[J]. Journal of the American Chemical Society, 2021, 143(42):17862-17870.
|
| [4] |
YAMATSUGU K, YIN L, KAMIJO S, et al. A synthesis of Tamiflu by using a barium-catalyzed asymmetric Diels-Alder-type reaction[J]. Angewandte Chemie, 2009, 121(6):1090-1096.
|
| [5] |
VANDAVASI J K, HUA X Y, BEN HALIMA H, et al. A nickel-catalyzed carbonyl-Heck reaction[J]. Angewandte Chemie International Edition, 2017, 56(48):15441-15445.
|
| [6] |
YANG Y, CHEN C, XU G Y, et al. An efficient nanocluster catalyst for Sonogashira reaction[J]. Journal of Catalysis, 2021, 401:206-213.
|
| [7] |
WANG Y H, WU Y F, LI Y H, et al. Denitrogenative Suzuki and carbonylative Suzuki coupling reactions of benzotriazoles with boronic acids[J]. Chemical Science, 2017, 8(5):3852-3857.
|
| [8] |
LIAO L L, WANG Z H, CAO K G, et al. Electrochemical ring-opening dicarboxylation of strained carbon-carbon single bonds with CO2:facile synthesis of diacids and derivatization into polyesters[J]. Journal of the American Chemical Society, 2022, 144(5):2062-2068.
|
| [9] |
ZHAO Y L, GUO X Q, LI S, et al. Transient stabilization effect of CO2 in the electrochemical hydrogenation of azo compounds and the reductive coupling of α-keto esters[J]. Angewandte Chemie International Edition, 2022, 61(48):e202213636.
|
| [10] |
WANG Y M, TAO M X, MO K M, et al. Palladium installed copper-organic framework for C — C coupling reactions[J]. Science China Chemistry, 2025, 68:1-7.
|
| [11] |
BULLOCK R M, CHEN J G, GAGLIARDI L, et al. Using nature’s blueprint to expand catalysis with Earth-abundant metals[J]. Science, 2020, 369(6505):eabc3183.
|
| [12] |
GHOLIPOUR B, SHOJAEI S, ROSTAMNIA S, et al. Metal-free nanostructured catalysts:sustainable driving forces for organic transformations[J]. Green Chemistry, 2021, 23(17):6223-6272.
|
| [13] |
YIN W Y, PAN X Z, LENG W X, et al. The highly efficient air oxidation of aryl and alkyl boronic acids by a microwave-assisted protocol under transition metal-free conditions[J]. Green Chemistry, 2019, 21(17):4614-4618.
|
| [14] |
IGARASHI T, TAYAMA E, IWAMOTO H, et al. Carbon-carbon bond formation via benzoyl umpolung attained by photoinduced electron-transfer with benzimidazolines[J]. Tetrahedron Letters, 2013, 54(50):6874-6877.
|
| [15] |
AHMED M R, CHENG Y K, NISHINA Y. Synthesis of visible-light-responsive nanocarbon and application for photocatalytic carbon-carbon bond formation[J]. Industrial & Engineering Chemistry Research, 2024, 63(16):7475-7480.
|
| [16] |
LE C C, MACMILLAN D W C. Fragment couplings via CO2 extrusion-recombination:expansion of a classic bond-forming strategy via metallaphotoredox[J]. Journal of the American Chemical Society, 2015, 137(37):11938-11941.
|
| [17] |
DHARA A K, MAITY S, DHAR B B. Visible-light-mediated synthesis of substituted phenazine and phenoxazinone using Eosin Y as a chotoredox catalyst[J]. Organic Letters, 2021, 23(9):3269-3273.
|
| [18] |
YAN D M, CHEN J R, XIAO W J. New roles for photoexcited Eosin Y in photochemical reactions[J]. Angewandte Chemie International Edition, 2019, 58(2):378-380.
|
| [19] |
DANG H T, HAUG G C, NGUYEN V T, et al. Acridine photocatalysis:insights into the mechanism and development of a dual-catalytic direct decarboxylative conjugate addition[J]. ACS Catalysis, 2020, 10(19):11448-11457.
|
| [20] |
DAS A, JUSTIN THOMAS K R. Rose-bengal photocatalyzed Knoevenagel condensation of aldehydes and ketones in aqueous medium[J]. Green Chemistry, 2022, 24(12):4952-4957.
|
| [21] |
YUAN F L, YUAN T, SUI L Z, et al. Engineering triangular carbon quantum dots with unprecedented narrow bandwidth emission for multicolored LEDs[J]. Nature Communications, 2018, 9(1):2249.
|
| [22] |
KONG J C, WEI Y H, ZHOU F, et al. Carbon quantum dots:properties, preparation, and applications[J]. Molecules, 2024, 29(9):2002.
|
| [23] |
TIAN L, LI Z, WANG P, et al. Carbon quantum dots for advanced electrocatalysis[J]. Journal of Energy Chemistry, 2021, 55:279-294.
|
| [24] |
BAIDILOV D, HAYRAPETYAN D, KHALIMON A Y. Recent advances in homogeneous base-metal-catalyzed transfer hydrogenation reactions[J]. Tetrahedron, 2021, 98:132435.
|
| [25] |
TRINCADO M, BANERJEE D, GRÜTZMACHER H. Molecular catalysts for hydrogen production from alcohols[J]. Energy & Environmental Science, 2014, 7(8):2464-2503.
|
| [26] |
LI S K, XIAO T F, LI D D, et al. First iridium-catalyzed highly enantioselective hydrogenation of β-nitroacrylates[J]. Organic Letters, 2015, 17(15):3782-3785.
|
| [27] |
NAKAMURA A, HAMASAKI A, GOTO S, et al. Irreversible catalytic ester hydrolysis of allyl esters to give acids and aldehydes by homogeneous ruthenium and ruthenium / palladium dual catalyst systems[J]. Advanced Synthesis & Catalysis, 2011, 353(6):973-984.
|
Funding
National Natural Science Foundation of China(21902023)
National Natural Science Foundation of China(21901252)
Shanghai Pujiang Program, China(19PJ1400300)
Professor of Special Appointment(Eastern Scholar)
Shanghai Institutions of Higher Education Fundamental Research Funds for the Central Universities, China(0900000155)
PDF
