Page 9 of 10
Journal of the American Chemical Society
(13) Xie, J.; Rudolph, M.; Rominger, F.; Hashmi, A. S. K. Angew. Chem.
(37) This count includes the electronically controlled HDF of benzoate
esters which provide access to the paraꢀHDF product, see ref. 11.
(38) Teegardin, K. A.; Weaver, J. D. Chem. Commun. 2017, 53, 4771.
(39) Day, J. I.; Weaver, J. D. J. Org. Chem. 2017, 82, 6801.
Int. Ed. 2017, 56, 7266.
1
2
(14) McTeague, T. A.; Jamison, T. F. Angew. Chem. Int. Ed. 2016, 55,
15072.
3
4
5
6
7
8
9
(15) Lu, J.; Khetrapal, N. S.; Johnson, J. A.; Zeng, X. C.; Zhang, J. J. Am.
Chem. Soc. 2016, 138, 15805.
(40) It is likely that the ammonium is in equilibrium with the free amine,
given the presence of the tertiary amine.
(41) a) Meyers, M. J.; Tortorella, M. D.; Xu, J.; Qin, L.; He, Z.; Lang, X.;
Zeng, W.; Xu, W.; Qin, L.; Prinsen, M. J.; Sverdrup, F. M.; Eickhoff, C.
S.; Griggs, D. W.; Oliva, J.; Ruminski, P. G.; Jacobsen, E. J.; Campbell,
M. A.; Wood, D. C.; Goldberg, D. E.; Liu, X.; Lu, Y.; Lu, X.; Tu, Z.; Lu,
(16) Singh, A.; Kubik, J. J.; Weaver, J. D. Chem. Sci. 2015, 6, 7206.
(17) Senaweera, S. M.; Weaver, J. D. J. Am. Chem. Soc. 2016, 138, 2520.
(18) Singh, A.; Fennell, C. J.; Weaver, J. D. Chem. Sci. 2016, 7, 6796.
(19) a) Selivanova, G. A.; Reshetov, A. V.; Beregovaya, I. V.; Vasil’eva,
N. V.; Bagryanskaya, I. Y.; Shteingarts, V. D. J. Fluorine Chem. 2012,
X.; Ding, K.; Chen, X. ACS Med. Chem. Lett. 2014, 5, 89 b) Malamas,
;
M. S.; Barnes, K.; Johnson, M.; Hui, Y.; Zhou, P.; Turner, J.; Hu, Y.;
Wagner, E.; Fan, K.; Chopra, R.; Olland, A.; Bard, J.; Pangalos, M.;
137, 64
;
b) Shteingarts, V. D. J. Fluorine Chem. 2007, 128, 797 c)
;
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
Mashkantsev, D. E.; Beregovaya, I. V.; Shchegoleva, L. N. J. Fluorine
Chem. 2016, 188, 171.
Reinhart, P.; Robichaud, A. J. Bioorg. Med. Chem. 2010, 18, 630 c)
;
(20) Shchegoleva, L. N.; Beregovaya, I. V.; Schastnev, P. V. Chem. Phys.
Lett. 1999, 312, 325.
Malamas, M. S.; Erdei, J.; Gunawan, I.; Barnes, K.; Hui, Y.; Johnson, M.;
Robichaud, A.; Zhou, P.; Yan, Y.; Solvibile, W.; Turner, J.; Fan, K. Y.;
Chopra, R.; Bard, J.; Pangalos, M. N. Bioorg. Med. Chem. Lett. 2011, 21,
(21) a) For examples of directed oxidative addition of metals see,
Sun, A. D.; Leung, K.; Restivo, A. D.; LaBerge, N. A.; Takasaki, H.;
Love, J. A. Chem. Eur. J. 2014, 20, 3162 c) Sun, A. D.; Love, J. A. Org.
;
b)
5164
;
d) Malamas, M. S.; Robichaud, A.; Erdei, J.; Quagliato, D.;
Solvibile, W.; Zhou, P.; Morris, K.; Turner, J.; Wagner, E.; Fan, K.;
;
Olland, A.; Jacobsen, S.; Reinhart, P.; Riddell, D.; Pangalos, M. Bioorg.
Lett. 2011, 13, 2750 d) Sun, A. D.; Love, J. A. Dalton Trans. 2010, 39,
10362 e) Sun, A. D.; Love, J. A. J. Fluorine Chem. 2010, 131, 1237 f)
Buckley, H. L.; Sun, A. D.; Love, J. A. Organometallics 2009, 28, 6622
;
Med. Chem. Lett. 2010, 20, 6597 e) Nowak, P.; Cole, D. C.; Aulabaugh,
;
;
;
A.; Bard, J.; Chopra, R.; Cowling, R.; Fan, K. Y.; Hu, B.; Jacobsen, S.;
Jani, M.; Jin, G.; Lo, M.ꢀC.; Malamas, M. S.; Manas, E. S.; Narasimhan,
R.; Reinhart, P.; Robichaud, A. J.; Stock, J. R.; Subrath, J.; Svenson, K.;
Turner, J.; Wagner, E.; Zhou, P.; Ellingboe, J. W. Bioorg. Med. Chem.
;
g) Chen, Z.; He, C.ꢀY.; Yin, Z.; Chen, L.; He, Y.; Zhang, X. Angew.
Chem. Int. Ed. 2013, 52, 5813.
Lett. 2010, 20, 632 f) Zhou, P.; Li, Y.; Fan, Y.; Wang, Z.; Chopra, R.;
;
(22) a) Dalvit, C.; Invernizzi, C.; Vulpetti, A. Chem. Eur. J. 2014, 20,
Olland, A.; Hu, Y.; Magolda, R. L.; Pangalos, M.; Reinhart, P. H.; Turner,
11058
A.; Desroches, J.; Paquin, J.ꢀF. Synthesis 2015, 47, 306.
(23) a) Hossain, M. A.; Saeed, M. A.; Pramanik, A.; Wong, B. M.;
Haque, S. A.; Powell, D. R. J. Am. Chem. Soc. 2012, 134, 11892 b)
Mason, S.; Llinares, J. M.; Morton, M.; Clifford, T.; BowmanꢀJames, K.
J. Am. Chem. Soc. 2000, 122, 1814 c) Hossain, A.; Llinares, J. M.;
;
b) Schneider, H.ꢀJ. Chem. Sci. 2012, 3, 1381
;
c) Champagne, P.
M. J.; Bard, J.; Malamas, M. S.; Robichaud, A. J. Bioorg. Med. Chem.
Lett. 2010, 20, 2326
;
g) Li, Z.; Zhou, M.; Wu, F.; Li, R.; Ding, Z. Eur. J.
h) Malamas, M. S.; Erdei, J.; Gunawan, I.;
Med. Chem. 2010, 46, 58
Turner, J.; Hu, Y.; Wagner, E.; Fan, K.; Chopra, R.; Olland, A.; Bard, J.;
;
;
Jacobsen, S.; Magolda, R. L.; Pangalos, M.; Robichaud, A. J. J. Med.
;
Chem. 2010, 53, 1146
10, 162.
;
i) Cruz, D. S.; Castilho, M. S. Med. Chem. 2014,
Mason, S.; Morehouse, P.; Powell, D.; BowmanꢀJames, K. Angew. Chem.,
Int. Ed. 2002, 41, 2335.
(42) Senaweera, S.; Weaver, J. D. J. Org. Chem. 2014, 79, 10466.
(43) The catalog number for the pyridine substrate is 300852 at Aspira
Chemical, and 809268 at SigmaꢀAldrich.
(44) Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165.
(45) a) Straathof, N. J. W.; Cramer, S. E.; Hessel, V.; Noël, T. Angew.
(24) a) The absolute hydration of fluoride has been measured to be
between ꢀ102 and ꢀ112 kcal/mol at 298 K. For comparison, hydration of
hydroxide is between ꢀ91 and ꢀ110 kcal/mol at 298 K, see ref., b) Zhan,
;
C.ꢀG.; Dixon, D. A. J. Phys. Chem. A 2004, 108, 2020.
(25) a) In related work, the addition of Lewis acids has been shown to
promote the oxidative addition of Niꢀcomplexes into CꢀF bonds, see b)
Baird, D. A.; Jamal, S.; Johnson, S. A. Organometallics 2017, 36, 1436.
Chem. Int. Ed. 2016, 55, 15549
Stephenson, C. R. J. Acc. Chem. Res. 2016, 49, 2295
Kreitmeier, P.; Reiser, O. Green Chem. 2016, 18, 214
Perez, A. C.; Collins, S. K. Acc. Chem. Res. 2016, 49, 1557
;
b) Staveness, D.; Bosque, I.;
;
;
;
c) Rackl, D.;
d) Hernandezꢀ
(26) When an average rate was determined in the photoꢀHDF reaction of
4b and N-Me-4b, ca. 45% conversion, a 3ꢀfold rate enhancement was
observed for 4b; see SIꢀ96 for details. .
(27) We performed a similar methylation/HDF vs HDF/methylation, or
alternative synthesis, experiment to confirm the difference in
regioselectivity for this substrate, see SIꢀ78.
(28) Laev, S. S.; Gurskaya, L. Y.; Selivanova, G. A.; Beregovaya, I. V.;
Shchegoleva, L. N.; Vasil’eva, N. V.; Shakirov, M. M.; Shteingarts, V. D.
Eur. J. Org. Chem. 2007, 2007, 306.
(29) Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem. Rev. 2013,
113, 5322.
(30) McDaniel, D. H.; Brown, H. C. J. Org. Chem. 1958, 23, 420.
(31) Additional substrates were screened, see SIꢀ57 for details.
(32) This compound was previously misassigned in our earlier work, see
ref 11.
(33) The trifluoroacetyl group is significantly more acidifying than the
acetyl group. This difference is reflected in both the pKa and the relative
downfield shift of the NH in the 1H NMR spectrum, see SIꢀ103 for
details.
(34) Sobkowski, M.; Stawinski, J.; Kraszewski, A. Nucleosides
Nucleotides Nucleic Acids 2010, 29, 628.
;
e) Cantillo,
D.; de Frutos, O.; Rincón, J. A.; Mateos, C.; Kappe, C. O. Org. Lett. 2014,
16, 896.
(46) Savile, C. K.; Janey, J. M.; Mundorff, E. C.; Moore, J. C.; Tam, S.;
Jarvis, W. R.; Colbeck, J. C.; Krebber, A.; Fleitz, F. J.; Brands, J.; Devine,
P. N.; Huisman, G. W.; Hughes, G. J. Science 2010, 329, 305.
(47) a) For alternative routes to the acid or sitaglipton, see b) Du Kim,
;
N.; Chang, J. Y.; Jung, J. H.; Lee, H. S.; Kim, D. J.; Chang, Y. K.; Lee, G.
S. Method for preparing intermediate of sitagliptin using chiral
oxirane.Google Patents.2011,
preparing 2,4,5ꢀtrifluorophenylacetic acid.Quzhou University, Peop. Rep.
China .2013, CN103012111A
;
c) Zheng, T.; Wu, G.; Lv, Y. Process for
.
(48) a) The orgin of 12a is not clear from the literature, but may proceed
via the perchlorination of benzonitrile, followed by partial Halex
fluorination, and hydrolysis of the nitrile, and then formation of the acid
chloride. To see a very similar sequence, see
Ban, C. Process for simple and safe preparation of pentafluorobenzoic
acid.Zhengzhou University, Peop. Rep. China .2006, CN1772724A
;
b) Niu, B.; Huang, Q.;
.
(35) Hutchby, M.; Houlden, C. E.; Haddow, M. F.; Tyler, S. N. G.;
LloydꢀJones, G. C.; BookerꢀMilburn, K. I. Angew. Chem. Int. Ed. 2012,
51, 548.
(36) MM2 minimization predicts the bulky amide will lead to a greater
degree of hydrogen bonding in the orthogonal direction, see SIꢀ94 for
details.
(49) The 3ꢀchloroꢀtetrafluorobenzoyl chloride cost $11.6/g from Alfa
Aesar on 4.14.17.
(50) For details pertaining to both syntheses, see SIꢀ48.
ACS Paragon Plus Environment