Academic Journal

Diboron-Enabled Nickel-Catalyzed Intermolecular Reductive Coupling of Styrenes With Aldehydes.

Λεπτομέρειες βιβλιογραφικής εγγραφής
Τίτλος: Diboron-Enabled Nickel-Catalyzed Intermolecular Reductive Coupling of Styrenes With Aldehydes.
Συγγραφείς: Yin HT; State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, Tianjin, China., Wang YQ; State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, Tianjin, China., Xiao LJ; State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, Tianjin, China.
Πηγή: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2026 Sep 29, pp. e71743. Date of Electronic Publication: 2026 Sep 29.
Publication Model: Ahead of Print
Τύπος έκδοσης: Journal Article
Γλώσσα: English
Στοιχεία περιοδικού: Publisher: Wiley-VCH Country of Publication: Germany NLM ID: 9513783 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1521-3765 (Electronic) Linking ISSN: 09476539 NLM ISO Abbreviation: Chemistry Subsets: MEDLINE
Imprint Name(s): Original Publication: Weinheim, Germany : Wiley-VCH
Περίληψη: The direct reductive coupling of alkenes with aldehydes offers an attractive alternative to conventional carbonyl addition using preformed organometallic reagents, yet intermolecular coupling of simple alkenes remains challenging. In this study, we report a diboron-enabled nickel-catalyzed reductive coupling of styrenes and related alkenes with aliphatic aldehydes to afford saturated alcohols with up to 93% yield and high linear regioselectivity. A diboron reagent/lithium methoxide (MeOLi) combination is crucial for productive coupling and enables broad functional-group tolerance. Deuterium-labeling and control experiments indicate that ethanol is the predominant hydrogen source and are consistent with a nickelacycle-based reductive pathway. This reaction establishes a complementary nickel-catalyzed manifold for direct alkene-aldehyde reductive coupling under mild conditions.
(© 2026 Wiley‐VCH GmbH.)
References: F. A. Carey and R. J. Sundberg, “Advanced Organic Chemistry, Part B: Reactions and Synthesis,” in Chapter “Reaction of Carbon Nucleophiles With Carbonyl Groups” (Springer).
J. Montgomery, “Nickel‐Catalyzed Reductive Cyclizations and Couplings,” Angewandte Chemie International Edition 43 (2004): 3890.
M. Kimura and Y. Tamaru, “Nickel‐Catalyzed Reductive Coupling of Dienes and Carbonyl Compounds,” Topics in Current Chemistry 279 (2007): 173.
P. Gandeepan and C. H. Cheng, “Cobalt Catalysis Involving π Components in Organic Synthesis,” Accounts of Chemical Research 48 (2015): 1194.
K. D. Nguyen, B. Y. Park, T. Luong, H. Sato, V. J. Garza, and M. J. Krische, “Metal‐Catalyzed Reductive Coupling of Olefin‐Derived Nucleophiles: Reinventing Carbonyl Addition,” Science 354 (2016): aah5133.
M. Holmes, L. A. Schwartz, and M. J. Krische, “Intermolecular Metal‐Catalyzed Reductive Coupling of Dienes, Allenes, and Enynes With Carbonyl Compounds and Imines,” Chemical Reviews 118 (2018): 6026.
R. Y. Liu and S. L. Buchwald, “CuH‐Catalyzed Olefin Functionalization: From Hydroamination to Carbonyl Addition,” Accounts of Chemical Research 53 (2020): 1229.
H. Xiao, G. Wang, and M. J. Krische, “Regioselective Hydrohydroxyalkylation of Styrene With Primary Alcohols or Aldehydes via Ruthenium‐Catalyzed C−C Bond Forming Transfer Hydrogenation,” Angewandte Chemie International Edition 55 (2016): 16119.
Y.‐L. Zheng, Y.‐Y. Liu, Y.‐M. Wu, Y.‐X. Wang, Y.‐T. Lin, and M. Ye, “Iron‐Catalyzed Regioselective Transfer Hydrogenative Couplings of Unactivated Aldehydes With Simple Alkenes,” Angewandte Chemie International Edition 55 (2016): 6315.
J. L. M. Matos, S. Vásquez‐Céspedes, J. Gu, T. Oguma, and R. A. Shenvi, “Branch‐Selective Addition of Unactivated Olefins Into Imines and Aldehydes,” Journal of the American Chemical Society 140 (2018): 16976.
M. Saladrigas, J. Puig, J. Bonjoch, and B. Bradshaw, “Iron‐Catalyzed Radical Intermolecular Addition of Unbiased Alkenes to Aldehydes,” Organic Letters 22 (2020): 8111.
Y. Hirao, Y. Katayama, H. Mitsunuma, and M. Kanai, “Chromium‐Catalyzed Linear‐Selective Alkylation of Aldehydes With Alkenes,” Organic Letters 22 (2020): 8584.
M. L. Czyz, T. H. Horngren, A. J. Kondopoulos, et al., “Photocatalytic Generation of Alkyl Carbanions From Aryl Alkenes,” Nature Catalysis 7 (2024): 1316.
Z. Li and A. Noble, “Aldehyde–Olefin Couplings by Photoinduced Reduction of Electron‐Deficient Olefins With Hantzsch Ester Anions,” Angewandte Chemie International Edition 65 (2026): e9744019.
H. Seo and T. F. Jamison, “Catalytic Generation and Use of Ketyl Radical From Unactivated Aliphatic Carbonyl Compounds,” Organic Letters 21 (2019): 10159.
D. Arnaldi, N. Intini, P. P. Sen, et al., “Intermolecular Reductive Coupling of Ketones and Alkenes Under Ferrioxalate Photocatalysis,” Journal of the American Chemical Society 148 (2026): 30553.
S. R. N. Kolusu, M. Rodríguez‐Martínez, C. Aira‐Rodríguez, et al., “Reductive Couplings via Nucleophilic Photoactivation of Carbonyls,” Journal of the American Chemical Society 148 (2026): 37235.
W. Yin, W. Wang, T.‐Y. Gao, et al., “Photocatalytic Reductive Coupling of Aliphatic Aldehydes With Alkenes,” Chinese Chemical Letters 38 (2026): 113236.
J. M. Edgecomb, S. N. Alektiar, N. G. W. Cowper, J. A. Sowin, and Z. K. Wickens, “Ketyl Radical Coupling Enabled by Polycyclic Aromatic Hydrocarbon Electrophotocatalysts,” Journal of the American Chemical Society 145 (2023): 20169.
L. J. Franov, T. L. Wilsdon, M. L. Czyz, and A. Polyzos, “Electroinduced Reductive and Dearomative Alkene‐Aldehyde Coupling,” Journal of the American Chemical Society 146 (2024): 29450.
E. P. Jackson, H. A. Malik, G. J. Sormunen, et al., “Mechanistic Basis for Regioselection and Regiodivergence in Nickel‐Catalyzed Reductive Couplings,” Accounts of Chemical Research 48 (2015): 1736.
E. A. Standley, S. Z. Tasker, K. L. Jensen, and T. F. Jamison, “Nickel Catalysis: Synergy Between Method Development and Total Synthesis,” Accounts of Chemical Research 48 (2015): 1503.
Y. Hoshimoto, M. Ohashi, and S. Ogoshi, “Catalytic Transformation of Aldehydes With Nickel Complexes Through η2 Coordination and Oxidative Cyclization,” Accounts of Chemical Research 48 (2015): 1746.
M.‐Y. Qian, K.‐X. Zhang, and L.‐J. Xiao, “Catalytic Transformations of Alkenes via Nickelacycles,” Organic Chemistry Frontiers 11 (2024): 4602.
W.‐J. Nan, Y.‐N. Duan, and L.‐J. Xiao, “Nickel‐Catalyzed Alkene–Imine Couplings via Nickelacycles,” Synthesis 58 (2025): 753.
Y. Hayashi, Y. Hoshimoto, R. Kumar, M. Ohashi, and S. Ogoshi, “Nickel(0)‐Catalyzed Intramolecular Reductive Coupling of Alkenes and Aldehydes or Ketones With Hydrosilanes,” Chemical Communications 52 (2016): 6237.
Y. Hayashi, Y. Hoshimoto, R. Kumar, M. Ohashi, and S. Ogoshi, “Nickel(0)‐Catalyzed Coupling Reactions of Carbonyls and Alkenes With Reducing Reagents Giving Six‑ and Seven‑Membered Benzocycloalkanols,” Chemistry Letters 46 (2017): 1096.
S. Ghosh, A. Rooj, R. Chakrabortty, and V. Ganesh, “Ni‑Catalyzed Diastereoconvergent Intramolecular Alkene–Aldehyde Reductive Coupling: A Route to Syn‑Chromanols,” Organic Letters 26 (2024): 4024.
X.‐Y. Sun, X.‐R. Liu, Y.‐W. Huang, Q.‐L. Zhou, and L.‐J. Xiao, “Diastereo‑ and Enantioselective Nickel‑Catalyzed Intramolecular Reductive Cyclization of Unactivated Alkenes and Aldehydes,” Organic Letters 28 (2026): 2512.
Y. Sato, M. Takimoto, K. Hayashi, T. Katsuhara, K. Takagi, and M. Mori, “Novel Stereoselective Cyclization via π‐Allylnickel Complex Generated from 1,3‐Diene and Hydride Nickel Complex,” Journal of the American Chemical Society 116 (1994): 9771.
M. Kimura, A. Ezoe, K. Shibata, and Y. Tamaru, “Novel and Highly Regio‐ and Stereoselective Nickel‐Catalyzed Homoallylation of Benzaldehyde With 1,3‐Dienes,” Journal of the American Chemical Society 120 (1998): 4033.
Y. Sato, Y. Hinata, R. Seki, Y. Oonishi, and N. Saito, “Nickel‐Catalyzed Enan‐tio‐ and Diastereoselective Three‐Component Coupling of 1,3‐Dienes, Aldehydes, and Silanes Using Chiral N‐Heterocyclic Carbenes as Ligands,” Organic Letters 9 (2007): 5597.
T. Q. Davies, J. Y. Kim, and A. Fürstner, “Nickel‐Catalyzed Enantioselective Coupling of Aldehydes and Electron‐Deficient 1,3‐Dienes Following an Inverse Regiochemical Course,” Journal of the American Chemical Society 144 (2022): 18817.
K.‐X. Zhang, M.‐Y. Liu, B.‐Y. Yao, Q.‐L. Zhou, and L.‐J. Xiao, “Stereoconvergent and Enantioselective Synthesis of Z‐Homoallylic Alcohols via Nickel‐Catalyzed Reductive Coupling of Z/E‐1,3‐Dienes With Aldehydes,” Journal of the American Chemical Society 146 (2024): 22157.
C. S. Buxton, D. C. Blakemore, and J. F. Bower, “Reductive Coupling of Acrylates with Ketones and Ketimines by a Nickel‐Catalyzed Transfer‐Hydrogenative Strategy,” Angewandte Chemie International Edition 56 (2017): 13824.
B. Xuan, M.‐Y. Qian, Q.‐L. Zhou, and L.‐J. Xiao, “Enantioselective Synthesis of γ‐Butyrolactones Bearing γ‐Quaternary Stereocenters via Nickel‐Catalyzed Reductive Coupling of Acrylates With Ketones,” Organic Letters 27 (2025): 8059.
M.‐Y. Qian, Y.‐Q. Wang, Q.‐L. Zhou, and L.‐J. Xiao, “Nickel‐Catalyzed Hydrocarbamoylation of Alkenes With Isocyanates,” Organic Letters 27 (2025): 2975.
B. Wang, T. Zhang, L.‐J. Xiao, and Q.‐L. Zhou, “Nickel‐Catalyzed Intermolecular Reductive Coupling of Styrene and Its Derivatives With Imines Using Methanol as a Reductant,” ACS Catalysis 13 (2023): 869.
Z.‐H. Chen, L.‐J. Gu, B. Wang, L.‐J. Xiao, M. Ye, and Q.‐L. Zhou, “Regioselective and Enantioselective Nickel‐Catalyzed Intermolecular Reductive Coupling of Aliphatic Alkenes With Imines,” Journal of the American Chemical Society 146 (2024): 14915.
T. Zhang, S. Jiang, M.‐Y. Qian, Q.‐L. Zhou, and L.‐J. Xiao, “Ligand‐Controlled Regiodivergent Nickel‐Catalyzed Hydroaminoalkylation of Unactivated Alkenes,” Journal of the American Chemical Society 146 (2024): 3458.
B. Wang, X.‐M. Liu, K.‐X. Zhang, W.‐M. Feng, L.‐J. Xiao, and Q.‐L. Zhou, “Diastereoselective and Enantioselective Nickel‐Catalyzed Reductive Coupling of Imines and Unactivated Alkenes,” CCS Chemistry 5 (2023): 814.
T. Zhang, Y.‐W. Huang, S.‐H. Cheng, et al., “Stereoselective Synthesis of Multisubstituted Cycloalkyl Amines via Nickel‐Catalyzed Intramolecular Hydroaminoalkylation,” CCS Chemistry 8 (2026): 2403.
S. Geng, C. Shi, B. Guo, H. Hou, Z. Liu, and Z. Feng, “Recent Progress in Transition‐Metal‐Catalyzed Reductive Cross‐Coupling Reactions Using Diboron Reagents as Reductants,” ACS Catalysis 13 (2023): 15469.
D. Sun, Y. Gong, Y. Wu, Y. Chen, and H. Gong, “Bis(Pinacolato)Diboron‐Enabled Ni‐Catalyzed Reductive Arylation/Vinylation of Alkyl Electrophiles,” Advanced Science 11 (2024): 2404301.
W. Li, Y. Zheng, Y. Gu, et al., “Bis(pinacolato)Diboron‐Enabled Nickel‐Catalyzed Regio‐ and Enantioselective Reductive [3+2] Annulation of β‐Bromoenones With Alkynes,” Angewandte Chemie International Edition 64 (2025): e202506873.
Z. Chen, G. Li, T. Zhu, et al., “B2Pin2‑Enabled Nickel/Brønsted Acid Relay‐Catalyzed Reductive [2+2+2] Cycloaddition: Facile Access to Unsymmetric Pentacyclic Pyridine Derivatives,” Organic Letters 27 (2025): 9631.
H. Shi, F. Wu, W. Zhu, et al., “B2Pin2‐Enabled Reductive Thioesterification of Aryl Triflates With Thiocarbonates,” Chemical Communications 61 (2025): 16652.
Y. Wu, X. Wang, Y. Han, et al., “Nickel‐Catalyzed Radical Relay Enabled Chemoselective Fluoroalkyl‐Borylation of [1.1.1]Propellane Under Kinetic Control,” Science Advances 12 (2026): eaea8588.
L. Zhao, C. Liu, J. Li, Y. Yuan, and X. Zeng, “Diboron‐Enabled Nickel‐Catalyzed Reductive Hydroperfluoroalkylation Toward β‐Perfluoroalkyl Carbonyls,” Organic Letters 28 (2026): 10353.
L. Lv and H. Qian, “Developments and Applications of Allyl‐(Aza)Allyl Coupling Reactions,” Green Synthesis and Catalysis 4 (2023): 190.
X.‐W. Han, T. Zhang, Y.‐L. Zheng, et al., “Brønsted Acid Enabled Nickel‐Catalyzed Hydroalkenylation of Aldehydes With Styrene and Derivatives,” Angewandte Chemie International Edition 57 (2018): 5068.
J. S. Marcum and S. J. Meek, “Efficient Enantio‐, Diastereo, E/Z‐, and Site‐Selective Nickel‐Catalyzed Fragment Couplings of Aldehydes, Dienes, and Organoborons,” Journal of the American Chemical Society 144 (2022): 19231.
J.‐T. Ma, T. Zhang, B.‐Y. Yao, L.‐J. Xiao, and Q.‐L. Zhou, “Diastereodivergent and Enantioselective Synthesis of Homoallylic Alcohols via Nickel‐Catalyzed Borylative Coupling of 1,3‐Dienes With Aldehydes,” Journal of the American Chemical Society 145 (2023): 19195.
S. Jiang, T. Zhang, X.‐Y. Luo, S. Dong, J.‐T. Ma, and L.‐J. Xiao, “Ligand‐Controlled Regiodivergent Carbosilylation of 1,3‐Dienes via Nickel‐Catalyzed Three‐Component Coupling Reactions,” Angewandte Chemie International Edition 64 (2025): e202504494.
J.‐T. Ma, B.‐Y. Yao, T. Zhang, et al., “Stereoselective Synthesis of Polyketide Motifs via Nickel‐Catalyzed Multicomponent Coupling of Aldehydes, Dienes, and Boronic Acids: Reaction Development and Mechanistic Insights,” Journal of the American Chemical Society 147 (2025): 45648.
S.‐Z. Tan, D.‐F. Zhang, L. Zhu, Q. Ouyang, W. Du, and Y.‐C. Chen, “Divergent Asymmetric Dialkylation of Dienoic Acids with Carbonyls and Zinc Reagents via Tandem Ni(0) and Ni(II) Catalysis,” Journal of the American Chemical Society 147 (2025): 20947.
X.‐R. Liu, X.‐Y. Luo, Y.‐Q. Wang, et al., “Nickel‐Catalyzed Enantioselective Direct Addition of 1,3‐Dienes to Aldehydes Enabled by Chiral Monodentate Diamidophosphite Ligands,” Angewandte Chemie International Edition 65 (2026): e2370635.
J.‐F. Li, Z.‐Z. Wei, Y.‐Q. Wang, and M. Ye, “Base‐Free Nickel‐Catalyzed Hydroboration of Simple Alkenes With Bis(Pinacolato)Diboron in an Alcoholic Solvent,” Green Chemistry 19 (2017): 4498.
Grant Information: 2022YFA1503200 National Key R&D Program of China; 22471134 National Natural Science Foundation of China; 63263152 Fundamental Research Funds for the Central Universities; 25HHWCSS00003 Haihe Laboratory of Sustainable Chemical Transformations; 25ZXZSSS00370 Tianjin Major Science and Technology Project for National Key Laboratories
Contributed Indexing: Keywords: aldehydes; alkenes; diboron reagents; nickel catalysis; reductive coupling
Entry Date(s): Date Created: 20260930 Latest Revision: 20260930
Update Code: 20260930
DOI: 10.1002/chem.71743
PMID: 42811386
Βάση Δεδομένων: MEDLINE
Περιγραφή
ISSN:1521-3765
DOI:10.1002/chem.71743