10.1002/ejoc.201701440
European Journal of Organic Chemistry
COMMUNICATION
K. L. Geisling, R. R. Miksch, S. M. Rappaport, Anal. Chem. 1982, 54,
140–142.
(c) M. Das, D. F. O’Shea, Chem. Eur. J. 2015, 21, 18717–18723. (d) M.
Das, D. F. O’Shea, Org. Lett. 2015, 17, 1962–1965. (e) M. Das, D. F.
O’Shea, J. Org. Chem. 2014, 79, 5595–5607.
[3]
[4]
[5]
I. Houson, Ed. Process Understanding: For Scale-Up and Manufacture
of Active Ingredients, Wiley, Weinheim, 2011.
[16] For other examples, see: (a) T. Sanji, S. Watanabe, T. Iyoda, Tetrahedron
Lett. 2016, 57, 1921–1924. (b) U. S. Dakarapu, A. Bokka, P. Asgari, G.
Trog, Y. Hua, H. H. Nguyen, N. Rahman, J. Jeon, Org. Lett. 2015, 17,
5792–5795. (c) R. Lerebours, C. Wolf, J. Am. Chem. Soc. 2006, 128,
13052–13053. (d) K. Yoshizawa, T. Shioiri, Tetrahedron Lett. 2006, 47,
757–761. (e) K. Yoshizawa, T. Shioiri, Tetrahedron Lett. 2005, 46, 7059–
7063.
G. Dequest, L. Bischoff, C. Fruit, F. Marssais, Org. Lett. 2007, 9, 1165–
1167.
Hydroxymethylation using A or B were utilized in the syntheses of natural
products. For recent examples, (a) H. Shi, C. Tan, W. Zhang, Z. Zhang,
R. Long, J. Gong, T. Luo, Z. Yang, J. Org. Chem. 2016, 81, 751–771. (b)
T. Asaba, Y. Katoh, D. Urabe, M. Inoue, Angew. Chem. Int. Ed. 2015, 54,
14457–14461; Angew. Chem. 2015, 127, 14665–14669. (c) H. Shi, C.
Tan, W. Zhang, Z. Zhang, R. Long, T. Luo, Z. Yang, Org. Lett. 2015, 17,
2342–2345.
[17] Conventionally, in the hydroxymethylation of trimethylsilyl arylacetylene,
the trimethylsilyl group is initially deprotected to form a terminal alkyne.
This is followed by the deprotonation of the formed terminal carbon-
hydrogen bond using a stoichiometric amount of base (n-BuLi or
LiHMDS) and coupling with formaldehyde sources. For examples, see:
(a) J. Takaya, Y. Miyashita, H. Kusama, N. Iwasawa, Tetrahedron 2011,
67, 4455–4466. (b) S. Kitagaki, Y. Okumura, C. Mukai, Tetrahedron 2006,
62, 10311–10320. (c) G. B. Jones, J. M. Wright, G. Hynd, J. K. Wyatt, P.
M. Warner, R. S. Huber, A. Li, M. W. Kilgore, R. P. Sticca, R. S. Pollenz,
J. Org. Chem. 2002, 67, 5727–5732. (d) M. A. Heut, S. K. Collins, G. P.
A. Yap, A. G. Fallis, Org. Lett. 2001, 3, 2883–2886.
[6]
[7]
M. Priede, M. Kazak, T. Kalnins, K. Shubin, E. Suna, J. Org. Chem. 2014,
79, 3715–3724.
As a related study, (hydroxymethyl)triphenylphosphonium salt generates
formaldehyde and triphenylphosphine in the presence of K2CO3 at room
temperature, which are used for subsequent Wittig olefinations with
benzylic and allylic halides. W. Huang, J. Xu, Synthetic Commun. 2015,
45, 1777–1782.
[8]
(a) M. A. Brook, Ed. Silicon in Organic, Organometallic, and Polymer
Chemistry, Wiley-Interscience, Weinheim, 2000. For examples of
reviews of transformations using organosilanes, see: (b) T. Komiyama,
Y. Minami, T. Hiyama, ACS Catal. 2017, 7, 631–651. (c) S. E. Denmark,
A. Ambrosi, Org. Process Res. Dev. 2015, 19, 982–994. (d) H. -J. Zhang,
D. L. Priebbenow, C. Bolm, Chem. Soc. Rev. 2013, 42, 8540–8571. (e)
S. E. Denmark, T. Y. Wilson, Angew. Chem. Int. Ed. 2012, 51, 9980–
9992; Angew. Chem. 2012, 124, 10120–10132. (f) Y. Nakao, T. Hiyama,
Chem. Soc. Rev. 2011, 40, 4893–4901.
[18]
Wolfe et al. have carried out the tetrabutylammonium fluoride (TBAF)-
mediated hydroxymethylation of trimethylsilylaryl acetylenes using
paraformaldehyde in a one-step procedure. However, this methodology
was applied to only two substrates (1c and trimethyl(naphthalen-2-
ylethynyl)silane). See: K. R. Everett, J. P. Wolfe, Org. Lett. 2013, 15,
2926–2929.
[19] Previously,
2 was synthesized by the reaction of N-trimethylsilyl
phthalimide and gaseous formaldehyde, see: V. P. Kozyukov, V. P.
Kozyukov, V. F. Mironov, Zh. Obshch. Khim., 1983, 53, 2091–2097. In
this study, we obtained 2 by the reaction of B and trimethylsilyl chloride
(Scheme S2).
[9]
For examples of the recently developed transition metal catalyzed
synthetic methods of organosilanes (not including the conventional
reactions of Grignard or organolithium reagents with silyl electrophiles),
see: (a) Z. Xu, W. -S. Huang, J. Zhang, L. -W. Xu, Synthesis 2015, 47,
3645–3668. (b) Q. Xiao, X. Meng, M. Kanai, Y. Kuninobu, Angew. Chem.
Int. Ed. 2014, 53, 3168–3172; Angew. Chem. 2014, 126, 3232–3236. (c)
C. Cheng, J. F. Hartwig, Science, 2014, 343, 853–857. (d) Y. Yamanoi,
H. Nishihara, J. Org. Chem. 2008, 73, 6671–6678. Organocatalysis: (e)
Y. Han, S. Zhang, J. He, Y. Zhang, J. Am. Chem. Soc. 2017, 139, 7399–
7407. (f) A. A. Toutov, W.-B. Liu, K. N. Betz, A. Fedorov, B. M. Stoltz, R.
H. Grubbs, Nature 2015, 518, 80–84. (g) M. Sasaki, Y. Kondo, Org. Lett.
2015, 17, 848–851. (h) P. Arde, V. Reddy, R. V. Anand, RSC Adv. 2014,
4, 49775–49779. (i) M. Yoshimatsu, M. Kuribayashi, J. Chem. Soc.
Perkin Trans. 1 2001, 1256–1257. Also see, (j) K. Nozawa-Kumada, M.
Inagi, Y. Kondo, Asian J. Org. Chem., 2017, 6, 63–66.
[20]
(a) Y. Araki, K. Kobayashi, M. Yonemoto, Y. Kondo, Org. Biomol. Chem.
2011, 9, 78–80. (b) H. Naka, D. Koseki, Y. Kondo, Adv. Synth. Catal.
2008, 350, 1901–1906. (c) M. Ueno, M. Yonemoto, M. Hashimoto, A. E.
H. Wheatley, H. Naka, Y. Kondo, Chem. Commun. 2007, 2264–2266. (d)
K. Suzawa,; M. Ueno, A. E. H. Wheatley, Y. Kondo, Chem. Commun.
2006, 4850–4852. (e) K. Kobayashi, M. Ueno, Y. Kondo, Chem.
Commun. 2006, 3128–3130. (f) M. Ueno, C. Hori, K. Suzawa, K. Ebisawa,
Y. Kondo, Eur. J. Org. Chem. 2005, 1965–1968.
[21] For related recent studies reported by other groups: (a) A. Kondo, T. Aoki,
M. Terada, Chem. Eur. J. 2017, 23, 2769-2773. (b) D. Jardel, C. Davies,
F. Peruch, S. Massip, B. Bibal, Adv. Synth. Catal. 2016, 358, 1110-1118.
(c) S. Okusu, K. Hirano, E. Tokunaga, N. Shibata, ChemistryOpen, 2015,
4, 581-585. (d) G.-F. Du, Y. Wang, C.-Z. Gu, B. Dai, L. He, RSC Adv.,
2015, 5, 35421-35424. (e) T. Punirum, D. Soorukram, C. Kuhakarn, V.
Reutrakul, M. Pohmakotr, Eur. J. Org. Chem., 2014, 4162-4169.
[10] For reviews, (a) R. L. Sutar, N. N. Joshi, Tetrahedron: Asymmetry 2013,
24, 1345–1363. (b) G. L. Beutner, S. E. Denmark, Angew. Chem. Int. Ed.
2013, 52, 9086–9096; Angew. Chem. 2013, 125, 9256–9266. (c) M. J.
Fuchter, Chem. Eur. J., 2010, 16, 12286–12294. (d) J. Gawronski, N.
Wascinska, J. Gajewy, Chem. Rev. 2008, 108, 5227–5252. (e) S. E.
Denmark, G. L. Beutner, Angew. Chem. Int. Ed. 2008, 47, 1560–1638;
Angew. Chem. 2008, 120, 1584–1663. (f) S. Y. Orito, M. Nakajima,
Synthesis, 2006, 1391–1401. (g) G. K. S. Prakash, A. K. Yudin, Chem.
Rev. 1997, 97, 757–786.
[22]
The reaction of 1a and 2 with 1 equiv. of t-Bu-P4 in DMF afforded 3a in
6% NMR yield.
[23]
As a related reaction, O-tert-butyldimethylsilylimidazoyl aminals are
deprotected to form aldehydes at room temperature in a HF-CH3CN
solution. T. Gimisis, P. Arsenyan, D. Georganakis, L. Leondiadis, Synlett,
2003, 1451.
[11]
(a) E. Nakamura, I. Kuwajima, Angew. Chem., Int. Ed. Engl. 1976, 15,
498–499; Angew. Chem. 1976, 88, 539. (b) I. Kuwajima, E. Nakamura,
K. Hashimoto, Tetrahedron 1983, 39, 975–982. (c) V. R. Chintareddy, K.
Wadhwa, J. Verkade, J. Org. Chem. 2011, 76, 4482–4488.
[24] When the reaction of 1a and 2 was quenched with saturated NH4Cl
aqueous solution instead of K2CO3 and MeOH, formation of V (R = Ph)
was confirmed by 1H-NMR and mass spectra analyses.
[12] R. B. Lettan II, K. A. Scheidt, Org. Lett. 2005, 7, 3227–3230.
[13] (a) T. Kitazawa, T. Minowa, T. Mukaiyama, Chem. Lett. 2006, 35, 1002–
1003. (b) H. Nagao, Y. Yamane, T. Mukaiyama, Chem. Lett. 2007, 36,
8–9. (c) M. Michida, T. Mukaiyama, Chem. Asian J. 2008, 3, 1592–1600.
(d) A. Capperucci, C. Tiberi, S. Pollicino, A. Degl’Innocenti, Tetrahedron
Lett. 2009, 50, 2808–2810.
[14] M. Hatano, E. Takagi, K. Ishihara, Org. Lett. 2007, 9, 4527-4530.
[15] (a) M. Das, A. Manvar, I. Fox, D. J. Roberts, D. F. O’Shea, Synlett 2017,
28, 2401–2406. (b) M. Das, D. F. O’Shea, Org. Lett. 2016, 18, 336–339.
This article is protected by copyright. All rights reserved.