Organometallics
Article
catalyst (0.0014 mmol, 1 mol %) were dissolved in C6D6 (0.5 mL),
and the solution was loaded into an NMR tube equipped with a J.
Young valve. The reaction mixture was allowed to react at ambient
temperature or 60 °C for 24 h, and the yield of cyclopentene was
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
■
S
1
determined by H NMR integration against the mesitylene standard.
Catalytic Rearrangement of 1-Phenyl-2-vinylcyclopropane
(12). In an N2-filled glovebox, 1-phenyl-2-vinylcyclopropane19 (29 mg,
0.20 mmol), mesitylene (24 mg, 0.20 mmol), and [i‑PrNDI]Ni2(C6H6)
(7.3 mg, 0.01 mmol, 5 mol %) were dissolved in C6D6 (0.5 mL), and
the solution was loaded into an NMR tube equipped with a J. Young
valve. The reaction mixture was allowed to react at 60 °C for 6 h, and
the yield of 3-phenylcyclopentene20 was determined by 1H NMR
integration against the mesitylene standard (93% yield). The crude
mixture was directly loaded on to an SiO2 column for purification
(mobile phase: pentane). 3-Phenylcyclopentene (13) was isolated in
Experimental details and characterization data (PDF)
Cartesian coordinates for calculated structures (XYZ)
Accession Codes
lographic data for this paper. These data can be obtained free of
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
1
52% yield (15 mg) as a colorless oil. H NMR (500 MHz, 295 K,
CDCl3) δ 7.33−7.28 (m, 2H, Ar H), 7.23−7.18 (m, 3H, Ar H), 5.96
(dq, J = 5.7, 2.3 Hz, 1H, CHCH), 5.80 (dq, J = 5.7, 2.1 Hz, 1H,
CHCH), 3.91 (m, 1H, CH), 2.58−2.47 (m, 1H, CH2), 2.47−2.37
(m, 2H, CH2), 1.79−1.69 (m, 1H, CH2). 13C{1H} NMR (126 MHz,
295 K, CDCl3) δ 146.5, 134.3, 131.9, 128.4, 127.2, 126.0, 51.4, 33.9,
32.5.
AUTHOR INFORMATION
Corresponding Author
ORCID
Notes
The authors declare no competing financial interest.
■
Catalytic Rearrangement of 1-Hexyl-2-vinylcyclopropane
(15). In an N2-filled glovebox, 1-hexyl-2-vinylcyclopropane (15.2 mg,
0.10 mmol), mesitylene (12 mg, 0.10 mmol), and [i‑PrNDI]Ni2(C6H6)
(7.3 mg, 0.01 mmol, 10 mol %) were dissolved in C6D6 (0.5 mL), and
the solution was loaded into an NMR tube equipped with a J. Young
valve. The reaction mixture was allowed to react at 80 °C for 24 h, and
the yield of 3-hexylcyclopentene21 was determined by 1H NMR
integration against the mesitylene standard (92% yield). The crude
mixture was directly loaded on to a SiO2 column for purification
(mobile phase: pentane). 3-Hexylcyclopentene (16) was isolated in
ACKNOWLEDGMENTS
■
This research was supported by the NSF (CHE-1554787) and
by Purdue University. C.U. is an Alfred P. Sloan Research
Fellow. X-ray diffraction data were collected using instruments
funded by the NSF (DMR-1337296).
1
58% yield (9 mg) as a colorless oil. H NMR (500 MHz, 295 K,
CDCl3) δ 5.69 (m, 2H, CHCH), 2.63 (br s, 1H), 2.30 (m, 2H),
2.03 (m, 1H), 1.35 (m, 11H, CH2), 0.89 (t, J = 6.6 MHz, 3H, CH3).
13C{1H} NMR (126 MHz, 295 K, C6D6) δ 135.5, 123.0, 45.6, 36.2,
32.0, 31.9, 29.9, 29.6, 28.0, 22.7, 14.1.
REFERENCES
■
(1) Recent reviews of transition metal catalyzed epoxide, aziridine,
and cyclopropane ring-opening reactions: (a) Jun, C.-H. Chem. Soc.
Rev. 2004, 33, 610−618. (b) Lu, B.-L.; Dai, L.; Shi, M. Chem. Soc. Rev.
2012, 41, 3318−3339. (c) Gao, Y.; Fu, X.-F.; Yu, Z.-X. Top. Curr.
Chem. 2014, 346, 195−232. (d) Tasker, S. Z.; Standley, E. A.; Jamison,
T. F. Nature 2014, 509, 299−309. (e) Huang, C.-Y.; Doyle, A. G.
Chem. Rev. 2014, 114, 8153−8198. (f) Chen, P.-H.; Billett, B. A.;
Tsukamoto, T.; Dong, G. ACS Catal. 2017, 7, 1340−1360.
(2) (a) Rybtchinski, B.; Milstein, D. Angew. Chem., Int. Ed. 1999, 38,
870−883. (b) Souillart, L.; Cramer, N. Chem. Rev. 2015, 115, 9410−
9464.
(3) (a) Tipper, C. F. H. J. Chem. Soc. 1955, 2045−2046. (b) Adams,
D. M.; Chatt, J.; Guy, R. G.; Sheppard, N. J. Chem. Soc. 1961, 0, 738−
742. (c) Schlodder, R.; Ibers, J. A.; Lenarda, M.; Graziani, M. J. Am.
Chem. Soc. 1974, 96, 6893−6900. (d) Lin, B. L.; Clough, C. R.;
Hillhouse, G. L. J. Am. Chem. Soc. 2002, 124, 2890−2891. (e) Ney, J.
E.; Wolfe, J. P. J. Am. Chem. Soc. 2006, 128, 15415−15422.
(f) Desnoyer, A. N.; Bowes, E. G.; Patrick, B. O.; Love, J. A. J. Am.
Chem. Soc. 2015, 137, 12748−12751.
(4) Zuo, G.; Louie, J. Angew. Chem., Int. Ed. 2004, 43, 2277−2279.
(5) Wang, S. C.; Troast, D. M.; Conda-Sheridan, M.; Zuo, G.;
LaGarde, D.; Louie, J.; Tantillo, D. J. J. Org. Chem. 2009, 74, 7822−
7833.
(6) Behlen, M. J.; Zhou, Y.-Y.; Steiman, T. J.; Pal, S.; Hartline, D. R.;
Zeller, M.; Uyeda, C. Dalton Trans. 2017, 46, 5493−5497.
(7) Hartline, D. R.; Zeller, M.; Uyeda, C. J. Am. Chem. Soc. 2017, 139,
13672−13675.
Catalytic Rearrangement of 17. In an N2-filled glovebox, 1722
(8.0 mg, 0.054 mmol), mesitylene (6.6 mg, 0.054 mmol), and
[
i‑PrNDI]Ni2(C6H6) (2 mg, 0.0027 mmol, 5 mol %) were dissolved in
C6D6 (0.5 mL), and the solution was loaded into an NMR tube
equipped with a J. Young valve. The reaction mixture was allowed to
1
react at 60 °C for 12 h, and the yield of 18 was determined by H
NMR integration against the mesitylene standard (83% yield). 1H
NMR (300 MHz, 295 K, C6D6) δ 7.87 (d, J = 8.8 Hz, 1H, −CHNPh),
7.25−6.98 (m, 5H, Ar H), 6.64−6.45 (m, 1H, −CHCHCH3), 5.87
(m, 1H, −CHCHCH3), 1.49 (d, J = 6.8 Hz, 3H, CH3).
Catalytic Rearrangement of 19. In an N2-filled glovebox,
cyclopropanecarboxaldehyde 19 (4.4 mg, 0.063 mmol), mesitylene
(7.6 mg, 0.063 mmol), and [i‑PrNDI]Ni2(C6H6) (5 mg, 0.0063 mmol,
10 mol %) were dissolved in C6D6 (0.5 mL), and the solution was
loaded into an NMR tube equipped with a J. Young valve. The
reaction mixture was allowed to react at 40 °C for 24 h, and the yield
1
of 20 was determined by H NMR integration against the mesitylene
standard (80% yield). 1H NMR (300 MHz, 295 K, CDCl3) δ 9.27 (d, J
= 6.7 Hz, 1H, −CHO), 6.03−5.77 (m, 2H, CHCH), 1.30 (d, J = 5.4
Hz, 3H, CH3).
Catalytic Rearrangement of 21. In an N2-filled glovebox, 1-
phenethylcyclopropan-1-ol23 21 (4.4 mg, 0.027 mmol), mesitylene
(3.3 mg, 0.027 mmol), and [i‑PrNDI]Ni2(C6H6) (2 mg, 0.0027 mmol,
10 mol %) were dissolved in C6D6 (0.5 mL), and the solution was
loaded into an NMR tube equipped with a J. Young valve. The
reaction mixture was allowed to react at 80 °C for 8 h, and the yield of
(8) Zhou, Y.-Y.; Hartline, D. R.; Steiman, T. J.; Fanwick, P. E.;
Uyeda, C. Inorg. Chem. 2014, 53, 11770−11777.
(9) Manuel, T. D.; Rohde, J.-U. J. Am. Chem. Soc. 2009, 131, 15582−
15583.
(10) Dong, Q.; Yang, X.-J.; Gong, S.; Luo, Q.; Li, Q.-S.; Su, J.-H.;
Zhao, Y.; Wu, B. Chem. - Eur. J. 2013, 19, 15240−15247.
2224 was determined by H NMR integration against the mesitylene
1
1
standard (86% yield). H NMR (400 MHz, 295 K, CDCl3) δ 7.32−
7.24 (m, 2H, Ar H), 7.19 (m, 3H, Ar H), 2.90 (t, J = 7.6 Hz, 2H,
CH2), 2.74 (t, J = 7.7 Hz, 2H, CH2), 2.40 (q, J = 7.3 Hz, 2H,
−CH2CH3), 1.04 (t, J = 7.3 Hz, 3H, −CH2CH3).
E
Organometallics XXXX, XXX, XXX−XXX