E
Synthesis
V. V. Levin et al.
Special Topic
1
H NMR (300 MHz, CDCl ): δ = 7.75 (d, J = 7.7 Hz, 4 H), 7.21 (d, J = 7.7
References
3
Hz, 4 H), 2.95 (s, 4 H), 1.37 (s, 24 H).
(1) (a) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117.
,2-Di(naphthalen-1-yl)ethane (2j)16
(b) Dilman, A. D.; Levin, V. V. Tetrahedron Lett. 2016, 57, 3986.
1
(c) The Chemistry of Organozinc Compounds; Rappoport, Z.;
Yield: 207 mg (99%); white solid; mp 150–157 °C.
Marek, I., Eds.; John Wiley Sons: Chichester, 2006.
&
1
H NMR (300 MHz, CDCl ): δ = 8.16 (d, J = 7.9 Hz, 2 H), 7.92 (d, J = 7.1
(d) Knochel, P.; Millot, N.; Rodrigues, A. L. Org. React. (N.Y.) 2001,
58, 417. (e) Knochel, P.; Jones, P. Organozinc Reagents: A Practi-
cal Approach; Oxford Medical Publications: Oxford, 1999.
3
Hz, 2 H), 7.78 (d, J = 7.9 Hz, 2 H), 7.61–7.49 (m, 4 H), 7.48–7.34 (m, 4
H), 3.55 (s, 4 H).
(
f) Erdik, E. Organozinc Reagents in Organic Synthesis; CRC Press:
[
1,1′-Bi(cyclohexane)]-2,2′-diene (2k)17
Boca Raton, 1996.
(
2) (a) Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem. Rev.
Yield: 115 mg (81% yield); colorless oil.
2013, 113, 5322. (b) Shaw, M. H.; Twilton, J.; MacMillan, D. W. C.
1
H NMR (300 MHz, CDCl ): δ (1:1 mixture of diastereoisomers) =
3
J. Org. Chem. 2016, 81, 6898. (c) Tucker, J. W.; Stephenson, C. R. J.
J. Org. Chem. 2012, 77, 1617. (d) Schultz, D. M.; Yoon, T. P.
Science 2014, 343, 1239176.
5
.79–5.68 (m, 2 H), 5.67–5.52 (m, 2 H), 2.22–2.06 (m, 2 H), 2.05–1.92
(m, 4 H), 1.84–1.64 (m, 4 H), 1.62–1.44 (m, 2 H), 1.43–1.25 (m, 2 H).
(
3) (a) Brooks, A. C.; Basore, K.; Bernhard, S. Inorg. Chem. 2013, 52,
2
,5-Diphenyl-hexa-1,5-diene (2l)18
5794. (b) Brooks, A. C.; Basore, K.; Bernhard, S. Chem. Commun.
Yield: 166 mg (95%); yellowish solid; mp 41–43 °C.
2014, 50, 5196.
1
(4) For photochemical homocoupling, see: (a) Park, G.; Yi, S. Y.;
H NMR (300 MHz, CDCl ): δ = 7.55–7.20 (m, 10 H), 5.30 (s, 2 H), 5.06
3
Jung, J.; Cho, E. J.; You, Y. Chem. Eur. J. 2016, 22, 17790.
(
s, 2 H), 2.67 (s, 4 H).
(b) Wiesner, S.; Walter, P.; Wagner, A.; Kaifer, E.; Himmel, H.-J.
Eur. J. Org. Chem. 2016, 5045.
(
2,2,3,3-Tetrafluorobutane-1,4-diyl)dibenzene (2m)
(
5) Conventional metal-mediated homocoupling is well known, for
selected examples, see: (a) Inaba, S.-i.; Matsumoto, H.; Rieke, R.
D. Tetrahedron Lett. 1982, 23, 4215. (b) Barrero, A. F.; Herrador,
M. M.; Quiez del Moral, J. F.; Arteaga, P.; Akssira, M.; El Hanbali,
F.; Arteaga, J. F.; Dieguez, H. R.; Sanchez, E. M. J. Org. Chem.
Yield: 127 mg (60%); white crystalline solid; mp 127.0–127.5 °C.
IR (film): 3031, 1496, 1456, 1438, 1352, 1246, 1158, 1085, 1051, 973,
9
–1
03, 767, 708, 540, 530 cm .
1
H NMR (300 MHz, CDCl ): δ = 7.42–7.30 (m, 10 H), 3.35 (tt, J = 20.2,
3
2007, 72, 2251. (c) Egorov, A. M.; Matyukhova, S. A.; Anisimov,
6
.3 Hz, 4 H).
A. V. Appl. Organomet. Chem. 2005, 19, 605. (d) Aitken, R. A.;
Hodgson, P. K. G.; Morrison, J. J.; Oyewale, A. O. J. Chem. Soc.,
Perkin Trans. 1 2002, 402. (e) Sato, K.; Inoue, Y.; Mori, T.;
Sakaue, A.; Tarui, A.; Omote, M.; Kumadaki, I.; Ando, A. Org. Lett.
1
3
C NMR (75 MHz, CDCl ): δ = 130.9, 128.4, 127.7, 118.0 (tt, J = 250.5,
3
3
7.7 Hz), 36.4 (m).
19
F NMR (282 MHz, CDCl ): δ = –114.0 (m, 4 F).
3
2
2
2
014, 16, 3756. (f) Liu, Y.; Xiao, S.; Qi, Y.; Du, F. Chem. Asian J.
017, 12, 673. (g) Cai, Y.; Qian, X.; Gosmini, C. Adv. Synth. Catal.
016, 358, 2427.
Anal. Calcd for C16H14F4: C, 68.08; H 5.00. Found: C, 67.97; H, 5.04.
1
,2,4-Triphenylbutane (5)
Benzylzinc bromide (1a) (0.6 mL of a 2.0 M solution in THF, 1.2 mmol,
.2 equiv), THF (0.6 mL), styrene (180 μL, 1.2 mmol, 1.2 equiv), benzyl
bromide (3a) (1.0 mmol, 1.0 equiv) and Ir(dtbbpy)(ppy) PF (1.75 mg,
(
6) For oxidative homocoupling of benzyl organometallics, see:
(
(
a) Zhu, Y.; Xiong, T.; Han, W.; Shi, Y. Org. Lett. 2014, 16, 6144.
b) Lei, A.; Zhang, X. Org. Lett. 2002, 4, 2285. (c) Hua, S.-K.; Hu,
1
2
6
Q.-P.; Ren, J.; Zeng, B.-B. Synthesis 2013, 45, 518. (d) Belter, R. K.
J. Fluorine Chem. 2015, 175, 110.
0.0025 equiv) were successively added to a test tube equipped with a
stir bar. The reaction mixture was stirred under irradiation with a
strip of 400 nm LEDs for 5 h, with water cooling to maintain the reac-
(
7) For single electron oxidation of organoboron and organosilicon
compounds under photoredox conditions, see: (a) Tellis, J. C.;
Kelly, C. B.; Primer, D. N.; Jouffroy, M.; Patel, N. R.; Molander, G.
A. Acc. Chem. Res. 2016, 49, 1429. (b) Matsui, J. K.; Lang, S. B.;
Heitz, D. R.; Molander, G. A. ACS Catal. 2017, 2563.
8) Levin, V. V.; Zemtsov, A. A.; Struchkova, M. I.; Dilman, A. D. Org.
Lett. 2013, 15, 917.
tion temperature around 23–25 °C. For the work-up, H O (5 mL) was
2
added and the mixture was extracted with hexane (3 × 7 mL). The
combined extracts were filtered through Na SO and concentrated
2
4
under vacuum. The residue was purified by flash chromatography
(
(
19
eluting with hexane to afford 1,2,4-triphenylbutane (5) (94 mg, 33%
yield) as a colorless oil, which solidified on storage; mp 28–29 °C.
9) Hatch, L. F.; Patton, T. L. J. Am. Chem. Soc. 1954, 76, 2705.
(10) Slinker, J. D.; Gorodetsky, A. A.; Lowry, M. S.; Wang, J.; Parker, S.;
1
H NMR (300 MHz, CDCl ): δ = 7.39–7.01 (m, 15 H), 3.01–2.86 (m, 3
3
H), 2.61–2.40 (m, 2 H), 1.93 (m, 2 H).
Rohl, R.; Bernhard, S.; Malliaras, G. G. J. Am. Chem. Soc. 2004,
126, 2763.
(11) Xie, P.; Xie, Y.; Qian, B.; Zhou, H.; Xia, C.; Huang, H. J. Am. Chem.
Soc. 2012, 134, 9902.
Funding Information
(12) Quast, H.; Kees, F. Chem. Ber. 1977, 110, 1780.
This work was supported by the Russian Foundation for Basic Re-
(13) Ledoussal, B.; Gorgues, A.; Le Coq, A. Tetrahedron 1987, 43,
search (project 16-29-10661).
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Bacsi
Research
1(6-29-1
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6
6
1)
5841.
(
14) Okazaki, Y.; Ando, F.; Koketsu, J. Bull. Chem. Soc. Jpn. 2003, 76,
155.
2
(15) Baltus, C. B.; Chuckowree, I. S.; Press, N. J.; Day, I. J.; Coles, S. J.;
Tizzard, G. J.; Spencer, J. Tetrahedron Lett. 2013, 54, 1211.
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–F