ACS Catalysis
Page 4 of 6
(2) Uraguchi, D.; Terada, M. J. Am. Chem. Soc. 2004, 126, 5356ꢀ
5357.
(3) For reviews, see: (a) Parmar, D.; Sugiono, E.; Raja, S.; Rueping,
M. Chem. Rev. 2014, 114, 9047ꢀ9153; (b) Lv, F.; Liu, S.; Hu, W.
Asian Journal of Organic Chemistry 2013, 2, 824ꢀ836; (c) Terada, M.
Chem. Commun. 2008, 4097ꢀ4112; (d) Zamfir, A.; Schenker, S.;
Freund, M.; Tsogoeva, S. B. Org. Biomol. Chem. 2010, 8, 5262ꢀ5276;
(e) Akiyama, T.; Itoh, J.; Fuchibe, K. Adv. Synth. Catal. 2006, 348,
999ꢀ1010; (f) Connon, S. J. Angew. Chem. Int. Ed. 2006, 45, 3909ꢀ
3912.
Under these conditions, the flow experiment was kept runꢀ
1
2
3
4
5
6
7
8
ning for 28 h, after which 4.60 g of 8a were isolated (92%
yield, 91% ee). These numbers amount to a total TON of 282
and a productivity of 2.22 mmol h–1 gresin–1. Remarkably, no
detectable decrease in the catalytic activity of the resin took
place in the 28 h experiment. This fact, together with the easy
reꢀactivation of PS-TRIP allows visualizing the small carꢀ
tridge containing only 0.5 g of catalyst as a micropilot plant,
suitable for the production of decimol amounts of enantiopure
homoallylic alcohol in short periods of time (ca. 90 h) with
highly reduced energy costs (no cooling required) and material
costs (in a flow process with a nonꢀdeactivating catalyst, the
TON increases linearly with time). Even more interestingly,
catalyst cartridges involving 5 to 50 g of PSꢀTRIP (amounts
within reach of the procedure reported herein) could be used
for kilogram production under very favourable cost and safety
conditions.
(4) (a) Hoffmann, S.; Seayad, A. M.; List, B. Angew. Chem. Int. Ed.
2005, 44, 7424ꢀ7427; (b) Rueping, M.; Sugiono, E.; Azap, C.;
Theissmann, T.; Bolte, M. Org. Lett. 2005, 7, 3781ꢀ3783; (c)
Rueping, M.; Antonchick, A. P.; Theissmann, T. Angew. Chem. Int.
Ed. 2006, 45, 3683ꢀ3686; (d) Rueping, M.; Antonchick, A. P. Angew.
Chem. Int. Ed. 2007, 46, 4562ꢀ4565; (e) Rueping, M.; Sugiono, E.;
Schoepke, F. R. Synlett 2010, 852ꢀ865; (f) Aillerie, A.; Talancé, V. L.
d.; Moncomble, A.; Bousquet, T.; Pélinski, L. Org. Lett. 2014, 16,
2982ꢀ2985.
(5) (a) Uraguchi, D.; Sorimachi, K.; Terada, M. J. Am. Chem. Soc.
2004, 126, 11804ꢀ11805; (b) Rueping, M.; Sugiono, E.; Theissmann,
T.; Kuenkel, A.; Köckritz, A.; PewsꢀDavtyan, A.; Nemati, N.; Beller,
M. Org. Lett. 2007, 9, 1065ꢀ1068; (c) Kang, Q.; Zhao, Z.ꢀA.; You, S.ꢀ
L. J. Am. Chem. Soc. 2007, 129, 1484ꢀ1485; (d) Rowland, G. B.;
Rowland, E. B.; Liang, Y.; Perman, J. A.; Antilla, J. C. Org. Lett.
2007, 9, 2609ꢀ2611; (e) Akiyama, T.; Honma, Y.; Itoh, J.; Fuchibe, K.
Adv. Synth. Catal. 2008, 350, 399ꢀ402; (f) Rueping, M.; Antonchick,
A. P. Org. Lett. 2008, 10, 1731ꢀ1734; (g) Li, G.; Kaplan, M. J.;
Wojtas, L.; Antilla, J. C. Org. Lett. 2010, 12, 1960ꢀ1963; (h) Enders,
D.; Seppelt, M.; Beck, T. Adv. Synth. Catal. 2010, 352, 1413ꢀ1418.
(6) (a) Jiang, J.; Yu, J.; Sun, X.ꢀX.; Rao, Q.ꢀQ.; Gong, L.ꢀZ. Angew.
Chem. Int. Ed. 2008, 47, 2458ꢀ2462; (b) Liu, H.; Dagousset, G.;
Masson, G.; Retailleau, P.; Zhu, J. J. Am. Chem. Soc. 2009, 131,
4598ꢀ4599; (c) Dagousset, G.; Zhu, J.; Masson, G. J. Am. Chem. Soc.
2011, 133, 14804ꢀ14813; (d) He, L.; Bekkaye, M.; Retailleau, P.;
Masson, G. Org. Lett. 2012, 14, 3158ꢀ3161; (e) Brioche, J.; Courant,
T.; Alcaraz, L.; Stocks, M.; Furber, M.; Zhu, J.; Masson, G. Adv.
Synth. Catal. 2014, 356, 1719ꢀ1724.
(7) (a) Čorić, I.; Müller, S.; List, B. J. Am. Chem. Soc. 2010, 132,
17370ꢀ17373; (b) Čorić, I.; Vellalath, S.; List, B. J. Am. Chem. Soc.
2010, 132, 8536ꢀ8537; (c) Sun, Z.; Winschel, G. A.; Borovika, A.;
Nagorny, P. J. Am. Chem. Soc. 2012, 134, 8074ꢀ8077; (d) Mensah, E.;
Camasso, N.; Kaplan, W.; Nagorny, P. Angew. Chem. Int. Ed. 2013,
52, 12932ꢀ12936; (e) Khomutnyk, Y. Y.; Argüelles, A. J.; Winschel,
G. A.; Sun, Z.; Zimmerman, P. M.; Nagorny, P. J. Am. Chem. Soc.
2015, 138, 444ꢀ456.
(8) Reid, J. P.; Goodman, J. M. J. Am. Chem. Soc. 2016, 138, 7910ꢀ
7917.
(9) Adair, G.; Mukherjee, S.; List, B. Aldrichimica Acta 2008, 41,
31ꢀ39.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
3. CONCLUSIONS
In summary, we have prepared a polystyreneꢀsupported
TRIP catalyst that has proven very active and enantioselective
in the allylation of aldehydes. The synthetic route, which
involves the coꢀpoymerization of a vinylated analog of the
TRIP diol, requires only three more steps than that of the
homogeneous counterpart and is amenable to multigram proꢀ
duction. The slightly longer synthesis is exceedingly compenꢀ
sated by the high recyclability of PS-TRIP, which has given
accumulated TONs in batch as high as 321 (the catalyst was
still active after 18 runs). The catalytic resin has also been put
to the test by means of a flow experiment spanning 28 h, in
which 4.60 g of allylated product were obtained (TON of 282,
productivity of 2.22 mmol h–1 gresin–1) without decrease in
activity. Thus, we believe that the recyclability and robustness
of PS-TRIP make it an interesting alternative to the already
successful homogeneous version.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website.
Synthetic procedures, characterization data, copies of NMR specꢀ
tra and HPLC chromatograms (PDF)
(10) (a) Mayer, S.; List, B. Angew. Chem. Int. Ed. 2006, 45, 4193ꢀ
4195; (b) Martin, N. J. A.; List, B. J. Am. Chem. Soc. 2006, 128,
13368ꢀ13369; (c) Wang, X.; List, B. Angew. Chem. Int. Ed. 2008, 47,
1119ꢀ1122; (d) Wang, X.; Reisinger, C. M.; List, B. J. Am. Chem.
Soc. 2008, 130, 6070ꢀ6071; for a review, see: (e) Mahlau, M.; List, B.
Angew. Chem. Int. Ed. 2013, 52, 518ꢀ533.
AUTHOR INFORMATION
Corresponding Authors
(11) Klussmann, M.; Ratjen, L.; Hoffmann, S.; Wakchaure, V.;
Goddard, R.; List, B. Synlett 2010, 2189ꢀ2192.
ACKNOWLEDGMENT
(12) For reviews on immobilization of (enantioselective) catalysts,
see: (a) Benaglia, M. Recoverable and Recyclable Catalysts; Wileyꢀ
VCH: Weinheim, 2009; (b) De Vos, D. E.; Vankelecom, I. F. J.;
Jacobs, P. A. Chiral Catalyst Immobilization and Recycling; Wileyꢀ
VCH: Weinheim, 2000; (c) Zamboulis, A.; Moitra, N.; Moreau, J. J.
E.; Cattoën, X.; Wong Chi Man, M. J. Mater. Chem. 2010, 20, 9322ꢀ
9338; (d) Cozzi, F. Adv. Synth. Catal. 2006, 348, 1367ꢀ1390; (e) Lu,
J.; Toy, P. H. Chem. Rev. 2009, 109, 815ꢀ838; (f) Kristensen, T. E.;
Hansen, T. Eur. J. Org. Chem. 2010, 3179ꢀ3204; (g) Benaglia, M.
New J. Chem. 2006, 30, 1525ꢀ1533; (h) Trindade, A. F.; Gois, P. M.
P.; Afonso, C. A. M. Chem. Rev. 2009, 109, 418ꢀ514; (i) Corma, A.;
Garcia, H. Adv. Synth. Catal. 2006, 348, 1391ꢀ1412; (j) Gruttadauria,
M.; Giacalone, F.; Noto, R. Chem. Soc. Rev. 2008, 37, 1666ꢀ1688.
This work was funded by the Institute of Chemical Research of
Catalonia (ICIQ) Foundation, MINECO (Grant CTQ2015ꢀ69136ꢀ
R and FPI preꢀdoctoral grant to L. C.ꢀA) and DEC Generalitat de
Catalunya (Grant 2014SGR827). We also thank MINECO for a
Severo Ochoa Excellence Accreditation 2014–2018 (SEVꢀ2013ꢀ
0319).
REFERENCES
(1) Akiyama, T.; Itoh, J.; Yokota, K.; Fuchibe, K. Angew. Chem.
Int. Ed. 2004, 43, 1566ꢀ1568.
ACS Paragon Plus Environment