DOI: 10.1126/science.287.5460.1995. Thermal, Catalytic, Regiospecific Functionalization of Alkanes

Thermal, Catalytic, Regiospecific Functionalization of Alkanes

10.1126/science.287.5460.1995

Crossref journal-article

American Association for the Advancement of Science (AAAS)

Science (221)

Abstract

The formation of a single product from terminal functionalization of linear alkanes from a transition metal–catalyzed reaction is reported. The rhodium complex Cp*Rh(η 4 -C 6 Me 6 ) (Cp*, C 5 Me 5 ; Me, methyl) catalyzes the high-yield formation of linear alkylboranes from commercially available borane reagents under thermal conditions. These reactions now allow catalytic, regiospecific functionalization of alkanes under thermal conditions. The organoborane products are among the most versatile synthetic intermediates in chemistry and serve as convenient precursors to alcohols, amines, and other common classes of functionalized molecules.

Bibliography

Chen, H., Schlecht, S., Semple, T. C., & Hartwig, J. F. (2000). Thermal, Catalytic, Regiospecific Functionalization of Alkanes. Science, 287(5460), 1995â1997.

Authors 4

Huiyuan Chen (first)
Sabine Schlecht (additional)
Thomas C. Semple (additional)
John F. Hartwig (additional)

References 35 Referenced 830

P. J. Chenier in Survey of Industrial Chemistry (VCH Weinheim 1992) p. 194 and p. 210.
10.1021/ja00276a025
10.1021/om00076a020
10.1021/ja00260a013
10.1021/ja983460p
W. W. Xu et al. Chem. Commun. (1997) p. 2273.
T. Sakakura and M. Tanaka J. Chem. Soc. Chem. Commun. (1987) p. 758. (10.1039/C39870000758)
H. C. Brown Organic Synthesis via Boranes (Wiley New York 1975). (10.1055/s-1975-23746)
A. Pelter K. Smith H. C. Brown Borane Reagents (Academic Press New York 1988).
10.1126/science.277.5323.211
10.1021/om990113v
10.1002/(SICI)1521-3773(19991115)38:22<3391::AID-ANIE3391>3.0.CO;2-N
C. N. Iverson and M. R. Smith [ J. Am. Chem. Soc. 121 7696 (1999)] have reported arene functionalization with three turnover numbers.
10.1021/ja00377a032
10.1021/ja00350a031
10.1021/ja00365a091
10.1021/ja00318a018
10.1021/cr9500085
D. Baudry M. Ephritikhine H. Felkin R. Holmes-Smith J. Chem. Soc. Chem. Commun. (1983) p. 788. (10.1039/c39830000788)
R. H. Crabtree and M. Lavin J. Chem. Soc. Chem. Commun. (1985) p. 1661.
10.1021/ja00298a018
P. M. Maitlis K. Moseley J. W. Kang J. Chem. Soc. A (1970) p. 2875.
This material is commercially available from several suppliers.
See Science Online (www.sciencemag.org/feature/data/1047762.shl) for literature references for catalyst preparations and previously prepared organoboranes along with spectroscopic data of new organoborane products.
10.1021/ja984409o
J. Ruiz B. E. Mann C. M. Spencer B. F. Taylor P. M. Maitlis J. Chem. Soc. Dalton Trans. (1987) p. 1963. (10.1039/DT9870001963)
10.1021/om00103a025
T. J. Marks and L. A. Shimp J. Am. Chem. Soc. 94 (1972) p. 1542. (10.1021/ja00760a018)
These measurements were conducted at roughly 20% conversion to prevent complication by the subsequent reaction of HBpin with octane.
10.1021/ic951504e
10.1021/ja9542451
10.1146/annurev.pc.33.100182.002425
10.1021/ja01624a023
T. Onak Organoborane Chemistry (Academic Press New York 1975) pp. 111–121. (10.1016/B978-0-12-526550-8.50009-5)
Supported by NSF grant CHE-9617171 and by Shell Chemicals. We thank Callery Chemicals for providing pinBBpin. S.S. thanks the Deutsche Forschungsgemeinschaft for a postdoctoral fellowship.

Dates

Type	When
Created	23 years, 1 month ago (July 27, 2002, 1:35 a.m.)
Deposited	1 year, 7 months ago (Jan. 13, 2024, 12:46 a.m.)
Indexed	1 week, 2 days ago (Aug. 28, 2025, 8:33 a.m.)
Issued	25 years, 5 months ago (March 17, 2000)
Published	25 years, 5 months ago (March 17, 2000)
Published Print	25 years, 5 months ago (March 17, 2000)

Funders 0

None

BibTeX

@article{Chen_2000, title={Thermal, Catalytic, Regiospecific Functionalization of Alkanes}, volume={287}, ISSN={1095-9203}, url={http://dx.doi.org/10.1126/science.287.5460.1995}, DOI={10.1126/science.287.5460.1995}, number={5460}, journal={Science}, publisher={American Association for the Advancement of Science (AAAS)}, author={Chen, Huiyuan and Schlecht, Sabine and Semple, Thomas C. and Hartwig, John F.}, year={2000}, month=mar, pages={1995–1997} }

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