DOI: 10.1002/cssc.200700142. Organic Carbonates as Alternative Solvents for Palladium‐Catalyzed Substitution Reactions

Organic Carbonates as Alternative Solvents for Palladium‐Catalyzed Substitution Reactions

10.1002/cssc.200700142

Crossref journal-article

Wiley

ChemSusChem (311)

Abstract

AbstractOrganic carbonates, such as propylene carbonate, butylene carbonate, and diethyl carbonate, were tested in the Pd‐catalyzed asymmetric allylic substitution reactions of rac‐1,3‐diphenyl‐3‐acetoxy‐prop‐1‐ene with dimethyl malonate or benzylamine as nucleophiles. Bidentate diphosphanes were used as chiral ligands. The application of monodentate phosphanes capable of self‐assembling with the metal was likewise tested. In the substitution reaction with dimethyl malonate, enantioselectivities up to 98 % were achieved. In the amination reaction, the chiral product was obtained with up to 83 % ee. The results confirm that these “green solvents” can be advantageously used for this catalytic transformation as an alternative to those solvents usually employed which run some risk of being harmful to the environment.

Bibliography

SchÃ¤ffner, B., Holz, J., Verevkin, S. P., & BÃ¶rner, A. (2008). Organic Carbonates as Alternative Solvents for PalladiumâCatalyzed Substitution Reactions. ChemSusChem, 1(3), 249â253. Portico.

Authors 4

Benjamin Schäffner (first)
Jens Holz (additional)
Sergey P. Verevkin (additional)
Armin Börner (additional)

References 63 Referenced 102

10.1002/ejic.200700405
10.1002/ange.200500368
10.1002/anie.200500368
10.1002/1521-3757(20021115)114:22<4350::AID-ANGE4350>3.0.CO;2-0
10.1002/1521-3773(20021115)41:22<4176::AID-ANIE4176>3.0.CO;2-U
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{'key': 'e_1_2_6_14_2', 'first-page': '1', 'volume': '50', 'author': 'Farina V.', 'year': '1997', 'journal-title': 'Org. React.'} / Org. React. by Farina V. (1997)
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{'key': 'e_1_2_6_23_2', 'volume-title': 'Green Reaction Media in Organic Synthesis', 'year': '2005'} / Green Reaction Media in Organic Synthesis (2005)
10.1021/ja026815k
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Boiling points: propylene carbonate (242 °C); butylene carbonate (244 °C); ethylene carbonate (247 °C).
For more information see:http://www.corporate.basf.com/en/sustainability/oekoeffizienz/label.htm.
I.Noriko Mitsubishi Chem. Corp. Patent JP7267 944 1995;
M. O. Ramin Dissertation (No. 16 676) ETH Zürich 2006.
10.1002/1438-9312(200203)104:3<161::AID-EJLT161>3.0.CO;2-N
10.1002/1615-4169(200212)344:10<1142::AID-ADSC1142>3.0.CO;2-P
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10.1023/A:1019078727850
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10.1002/anie.200700990
10.1016/j.tetlet.2007.11.199
Phanephos=4 12‐bis(diphenylphosphanyl)‐[2.2]‐paracyclophane (7); Tol‐binap=2 2′‐bis(di‐p‐tolylphosphanyl)‐1 1′‐binaphthyl (8); Me‐phox=2‐[2‐(diphenylphosphanyl)phenyl]‐4‐methyl‐4 5‐dihydrooxazole (9); Me‐Duphos=1 2‐bis‐(2 5‐dimethylphospholano)benzene (10); binaphane=1 2‐bis(4 5‐dihydro‐3H‐binaphtho[1 2‐c:2′ 1′‐e]phosphepino)benzene (11); DPhDPhPPr=1 3‐diphenyl‐1 3‐diphenylphosphanylpropane (12); bppm=N‐Boc‐4‐diphenylphosphanyl‐diphenylphosphanyl methylpyrrolidine (13); Tol‐MeO‐biphep=6 6′‐dimethoxy‐2 2′‐bis(diphenylphosphanyl)‐1 1′‐biphenyl (14); CF3‐xylyl‐walphos=1‐[2‐(2′‐diphenylphosphanylphenyl)ferrocenyl]ethyldi(bis‐3 5‐trifluoromethylphenyl)phosphane (15); Me‐phospholane=2 5‐dimethyl‐1‐(1H‐pyridin‐6‐on‐2‐yl)phospholane (16); Ph‐phospholane=2 5‐dimethyl‐1‐(1H‐pyridin‐6‐on‐2‐yl)‐phospholane (17); phosphepine=(1H‐pyridin‐6‐on‐2‐yl)‐phosphepine (18).
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10.1039/b100903f

Dates

Type	When
Created	17 years, 6 months ago (Feb. 20, 2008, 12:04 p.m.)
Deposited	1 year, 10 months ago (Oct. 11, 2023, 12:13 a.m.)
Indexed	4 days, 12 hours ago (Aug. 29, 2025, 6:14 a.m.)
Issued	17 years, 5 months ago (March 17, 2008)
Published	17 years, 5 months ago (March 17, 2008)
Published Online	17 years, 5 months ago (March 17, 2008)
Published Print	17 years, 5 months ago (March 25, 2008)

Funders 0

None

BibTeX

@article{Sch_ffner_2008, title={Organic Carbonates as Alternative Solvents for Palladium‐Catalyzed Substitution Reactions}, volume={1}, ISSN={1864-564X}, url={http://dx.doi.org/10.1002/cssc.200700142}, DOI={10.1002/cssc.200700142}, number={3}, journal={ChemSusChem}, publisher={Wiley}, author={Schäffner, Benjamin and Holz, Jens and Verevkin, Sergey P. and Börner, Armin}, year={2008}, month=mar, pages={249–253} }

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      "group": {
        "name": "publication_history",
        "label": "Publication History"
      }
    },
    {
      "value": "2008-03-17",
      "order": 2,
      "name": "published",
      "label": "Published",
      "group": {
        "name": "publication_history",
        "label": "Publication History"
      }
    }
  ]
}