Silver-mediated oxidative functionalization of alkylsilanes

Article abstract of DOI:10.1039/c8sc03730b

A general approach to the functionalization of aliphatic C-Si bonds in the presence of silver salts and oxidants has been reported. This strategy encompasses a range of valuable C-Si transformations, including the direct conversions of a C-Si bond to C-OCF₃, C-OBz, C-OCOCF₃, C-SCF₃, C-SCN, and C-N₃ bonds. Among them, trifluoromethoxylation of alkylsilanes is reported for the first time. In addition, mechanistic studies indicate that this reaction may proceed through a radical mechanism.

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Silver-Mediated Oxidative Functionalization of
Alkylsilanes
Cite this: DOI: 10.1039/x0xx00000x
Feng Wang, ‡, a Peng Xu, ‡, a Fei Conga and Pingping Tang*a
Received 00th January 2012,
Accepted 00th January 2012
A general approach to the functionalization of aliphatic CꢀSi bonds in the presence of silver salt and
oxidant has been reported. This strategy encompasses a range of valuable CꢀSi transformations,
including the direct conversions of a CꢀSi bond to CꢀOCF3, CꢀOBz, CꢀOCOCF3, CꢀSCF3, CꢀSCN, CꢀN3
bonds. Among them, trifluoromethoxylation of alkylsilanes is reported in the first time. In addition,
mechanistic studies indicate that the reaction may proceed through a radical mechanism.
DOI: 10.1039/x0xx00000x
www.rsc.org/
Organosilicon compounds have a multitude of applications in basic new trifluoromethoxylation reagent by Hu group, and was used to
science, medicine, and industry due to their stability, nonꢀtoxicity, prepare trifluoromethyl ether from trifluoromethoxylationꢀ
and natural abundance of silicon.1 For example, organosilicon halogenation of arynes, which was generated in situ from oꢀ
compounds have been received much attention to the crossꢀcoupling trimethylsilylphenyl triflate.7g Despite the advances of these
reaction.2 However, the strategic functionalization of aliphatic methods, trifluoromethoxylation of alkylsilanes was not reported to
carbonꢀsilicon bonds is limited.3 For example, trifluoromethoxy date, so the development of a general approach for functionalization
(OCF3) group and trifluoromethylthio (SCF3) group are becoming including trifluoromethoxylation of alkylsilanes is highly desirable.
increasingly important in medicinal, agrochemical and materials
Inspired by our previous work of a hypervalent iodineꢀmediated
science due to their strong electronꢀwithdrawing effect and high fluorination of alkylsilanes using fluoride ions as the fluorinating
lipophilicity.4 Thus, the development of efficient methods for the agent,9e we became interested in the possibility of functionalization
synthesis of OCF3 and SCF3 compounds is of great importance.5,6
Table 1. Optimizing reaction conditions.a
However, the trifluoromethoxylation and trifluoromethylthiolation of
organosilanes are extremely underdeveloped.7 To the best of our
knowledge, no trifluoromethoxylation of alkylsilanes has been
reported to date. Herein, we sought a strategy that would facilitate
the direct conversion of aliphatic CꢀSi bonds into a variety of
functional groups, including the trifluoromethoxylation and
trifluoromethylthiolation of alkylsilanes (Scheme 1).
–OCF3 or
–SCF3
Yield
(%)c
entry
Ligand
Oxidant
1
2
Et3N•3HF, TFMS (2)
CsF, TFMS (2)
TBAF, TFMS (2)
FeF3, TFMS (2)
AgF, TFMS (2)
AgF, TFMS (2)
AgF, TFMS (2)
AgF, TFMS (2)
AgF, TFMS (2)
AgF, TFMS (2)
AgF, TFMS (2)
AgF, TFMS (2)
AgF, TFMS (2)
AgF, TFMS (2)
AgSCF3
3,4,7,8-Me4-Phen
3,4,7,8-Me4-Phen
3,4,7,8-Me4-Phen
3,4,7,8-Me4-Phen
3,4,7,8-Me4-Phen
Phen
Selectfluor
Selectfluor
Selectfluor
Selectfluor
Selectfluor
Selectfluor
Selectfluor
Selectfluor
Selectfluor
Selectfluor
NFSI
3a, 0
3a, 0
3a, 0
3a, 0
3a, 61
3a, 45
3a, 8
3a, 52
3a, 2
3a, 56
3a, 0
3a, 0
3a, 0
3a, 0
3b, 80
3
4
5
6
7
neocuproine
8
4,7-Ph2-Phen
5,6-dione-Phen
dtbpy
9
10
11
12
13
14
15[b]
Scheme 1. Silverꢀmediated oxidative functionalization of alkylsilanes.
3,4,7,8-Me4-Phen
3,4,7,8-Me4-Phen
3,4,7,8-Me4-Phen
3,4,7,8-Me4-Phen
dtbpy
PhIO
PhI(OAc)2
K2S2O8
Methods for aliphatic C−Si oxidation,8 halogenation,9 and azꢀ
idation10 have been reported, but new reaction systems are typically
required to promote each transformation. In addition, methods for
trifluoromethoxylation of organosilanes are rare, and only two
examples were reported. In 2008, using trifluoromethyl triflate as the
trifluoromethoxylation reagent, Kolomeitsev group reported the
trifluoromethoxylation of arynes from oꢀtrimethylsilylphenylꢀ
Selectfluor
a General conditions: 1 (1.0 equiv), silver salt (4.0 equiv), TFMS (2) (5.0
equiv), ligand (0.3 equiv), oxidant (3.0 equiv), MeCN/DCM (v/v 7:2), 25 °C,
N2. b AgSCF3 (4.0 equiv), CsF (4.0 equiv), dtbpy (0.4 equiv), Selectfluor (3.0
equiv), MeCN/dioxane (v/v 1:1), 50 °C, N2. c Yields were determined by 19
F
triflate.7a In 2018, trifluoromethyl benzoate (TFBz) was reported as a NMR with benzotrifluoride as a standard.
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Table 2. Substrate scope for silverꢀmediated oxidative trifluoromethoxylation and trifluoromethylthiolation of alkylsilanes
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a Condition A: alkylsilanes (1.0 equiv), AgF (4.0 equiv), 3,4,7,8ꢀtetramethylꢀ1,10ꢀphenanthroline (0.3 equiv), Selectfluor (3.0 equiv), TFMS (2) (5.0 equiv),
MeCN/DCM (v/v 7:2), N2 atmosphere, 25°C. Condition B: alkylsilanes (1.0 equiv), AgSCF3 (4.0 equiv), 4,4’ꢀdiꢀtertꢀbutylꢀ2,2’ꢀbipyridine (0.4 equiv),
Selectfluor (3.0 equiv), CsF (4.0 equiv), MeCN/dioxane (v/v 1:1), N2 atmosphere, 50°C. Yields of isolated products are given. b25 °C was used. c MeCN/DCM
(v/v 1:1) was used. d Yield was determined by 19F NMR with benzotrifluoride as a standard.
of alkylsilanes using other nucleophiles such as –OCF3. Recently,
trifluoromethyl arylsulfonate (TFMS) as new trifluoroꢀ with low yields (37, 38), and alkenes were the major byproducts.
trifluoromethylthiolation of secondary alkylsilanes were observed
a
methoxylation reagent was disclosed by our group, which was used
to generate AgOCF3 in situ in the presence of silver salts and
fluoride ions.11 Thus, we envisioned whether the oxidative trifluoꢀ
romethoxylation of alkylsilanes could be achieved with –OCF3 which
was generated in situ in the presence of fluoride ions and TFMS.
Initial investigations focused on the reaction of alkylsilane 1 with
various fluorine sources in the presence of trifluoromethyl 4ꢀ
methylbenzenesulfonate (TFMS, 2) (Table 1, see more details in the
Supporting Information). No desired product 3a was observed when
Et3N•3HF, CsF, TBAF or FeF3 was used as the fluoride ion sources
(Table 1, entries 1ꢀ4). We were delighted to find that 61% yield of
the desired product 3a was observed in the presence of AgF (Table 1,
entry 5). Different ligands were evaluated and 3,4,7,8ꢀtetramethylꢀ
1,10ꢀphenanthroline gave the highest yield (Table 1, entries 5ꢀ10).
Switching to the other oxidants such as Nꢀfluorobenzenesulfonimide
(NFSI), PhIO, PhI(OAc)2, K2S2O8 could not generate 3a (Table 1,
entries 11ꢀ14). No desired products were detected in control
experiments with AgF or oxidant omitted. After extensive screening
of various solvents, different substitution on TFMS, and
temperatures (see more details in the Supporting Information), the
ideal conditions of 4.0 equiv of AgF, 0.3 equiv of 3,4,7,8ꢀ
tetramethylꢀ1,10ꢀphenanthroline, 3.0 equiv of Selectfluor, 5.0 equiv
of TFMS (2) in 7:2 (v:v) MeCN/DCM under N2 atmosphere at 25°C
were found to produce the highest yields. Encouraged by these
Table 3. Substrate scope for silverꢀmediated oxidative functionalization of
alkylsilanes.
a
1 (1.0 equiv), AgOBz (4.0 equiv), CsF (4.0 equiv), ligand (0.4 equiv),
Selectfluor (3.0 equiv), MeCN/DCE (v/v 1:1), 50 °C, N2. b 1 (1.0 equiv),
AgOCOCF3 (4.0 equiv), CsF (4.0 equiv), ligand (0.4 equiv), Selectfluor (3.0
equiv), DMC, 50 °C, N2. c 1 (1.0 equiv), AgSCN (4.0 equiv), CsF (4.0 equiv),
ligand (0.4 equiv), Selectfluor (3.0 equiv), MeCN/DCE (v/v 1:1), 50 °C, N2. d
results, we successfully extended the present system to
a
trifluoromethylthiolation of alkylsilanes by changing the ligand and
silver salt. After optimization of the reaction conditions, the desired 1 (1.0 equiv), AgF (4.0 equiv), TsN3 (4.0 equiv), ligand (0.4 equiv),
Selectfluor(II) (3.0 equiv), MeCN/DCE/EtOH (v/v/v 5:5:1), 25 °C, N2.
trifluoromethylthiolated product (3b) was observed in 80% yield
under 4.0 equiv of AgSCF3, 0.4 equiv of 4,4’ꢀdiꢀtertꢀbutylꢀ2,2’ꢀ
bipyridine, 3.0 equiv of Selectfluor, 4.0 equiv of CsF in 1:1 (v:v)
MeCN/dioxane under N2 atmosphere at 50 °C (Table 1, entry 15, see
more details in the Supporting Information).
Encouraged by our success with trifluoromethoxylation and triꢀ
fluoromethylthiolation of alkylsilanes, we investigated the use of
other silver salt to develop the functionalization of alkylsilanes
(Table 3). When AgOBz, AgOCOCF3, or AgSCN was used, the
corresponding products (42, 43, 44) were obtained in moderate
yields. Installation of an azide group have proven to be useful in
chemical biology, medicinal chemistry, and materials science.12 The
use of AgF and TsN3 enabled azidation of alkylsilanes 1 to prepare
the desired product 45 in 63% isolated yield. We note that in each
system, both the silver salt and oxidant were necessary for
productive reactivity. Although these reactions are not fully
optimized, they provide a general strategy for the functionalization
of alkylsilanes.
To gain some insight into the reaction mechanism, we performed
some preliminary studies (Scheme 2a). Less than 10% triꢀ
fluoromethoxylated or trifluoromethylthiolated product was formed
when a radical inhibitor 2,6ꢀdiꢀtertꢀbutylꢀ4ꢀmethylphenol (BHT) (8
equiv) was added. In addition, When 4 equiv of 2,2,6,6ꢀtetramethylꢀ
1ꢀpiperidinyloxy (TEMPO) was added, the TEMPO adduct 46 or 47
was obtained in 25% and 38% isolated yield, respectively.
Furthermore, the reaction of alkene silanes under the standard
reaction conditions (condition B) gave the trifluoromethylthiolated
product 48 (37%) accompanied with the 5ꢀexoꢀcyclization
trifluoromethylthiolated product 48’ in 12% yield. Together, these
observations strongly suggested that a radicalꢀchain mechanism or
singleꢀelectron transfer (SET) was involved in the reactions. In
addition, 28% trifluoromethoxylated products was observed when
AgF2 was used in the absence of AgF and Selectfluor, which
indicated that Ag(II) species could be involved in the reaction (see
Having established optimized reaction conditions, we then exꢀ
plored the scope of trifluoromethoxylation and trifluoromethylthiꢀ
olation with structurally diverse alkylsilanes. As displayed in Table
2, a wide range of primary alkylsilanes bearing electronꢀdonating
and electronꢀwithdrawing substituents on aryl rings were
successfully converted into the desired trifluoromethoxylated and
trifluoromethylthiolated products with good isolated yields (4 to 16).
Notably, heteroaromatic substrates, such as pyridine, indole, and
thiophene were also successfully employed to provide the correꢀ
sponding trifluoromethoxylated and trifluoromethylthiolated
products (17 to 21). A good range of functional groups including
ester, ether, ketone, nitrile, nitro, amide, chloride, bromide, and even
iodide were well tolerated under the mild reaction conditions.
Moreover, the trifluoromethylthiolation of alkylsilane with tertiary
alcohol also proceeded smoothly (36). These results encouraged the
application of this method to more complex small molecules, which
gave
the
corresponding
trifluoromethoxylated
and
trifluoromethylthiolated products in moderate yields (39, 40, 41).
For example, the alkylsilane derived from celecoxib, which is a
nonsteroidal antiꢀinflammatory drug, were converted to the triꢀ
fluoromethoxylated product (40a) in 31% yield, or trifluorome
thylthiolated product (40b) in 57% yield. In addition, we prepared
compound 5a, 5b in gram scale under the standard reaction condiꢀ
tions in 44%, 69% isolated yield, respectively, which demonstrates
the scalability of this method. However, trifluoromethoxylation and
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more details in the Supporting Information). Finally, silver mirror arylsulfonate (TFMS) as the trifluoromethoxylation reagent.
was observed in the reaction, which suggested that Ag(0) was Additionally, preliminary mechanistic studies suggested that the
generated.
reaction may proceed through a radical mechanism.
On the basis of these mechanistic investigations, we proposed the
mechanism depicted in Scheme 2b. In the presence of ligand and
Selectfluor, AgFG (FG = OCF3, OBz, OCOCF3, SCF3, SCN, N3) is
oxidized to produce Ag(II) intermediated I,11d then R group
transmetalation from silicon to Ag(II) intermediated I can afford
alkylsilver species II. The subsequent singleꢀelectron transfer
between Ag(II) and R group in intermediated II leads to the genꢀ
eration of R radical and Ag(I) species III. Finally, the FG group
transfer from the intermediated III to R radical generates RFG and
Ag(0). At present, we cannot rule out the possibility of an alternaꢀ
tive mechanism that R radical intermediate is further oxidized to
generate R carbocation intermediate, which is trapped by FG anion
to form the desired product.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
We gratefully acknowledge the State Key Laboratory of Elementoꢀ
Organic Chemistry for generous startꢀup financial support. This
work was supported by the National Key Research and Development
Program of China (2016YFA0602900), and the National Natural
Science Foundation of China (21522205, 21672110) and the
Fundamental Research Funds for the Central Universities.
Notes and references
a
State Key Laboratory and Institute of ElementoꢀOrganic Chemistry,
College of Chemistry, Collaborative Innovation Center of Chemical
Science and Engineering (Tianjin), Nankai University, Tianjin 300071,
China
Eꢀmail: ptang@nankai.edu.cn.
† Electronic Supplementary Information (ESI) available: Data for new
compounds and experimental procedures. See DOI: 10.1039/c000000x/
‡ These authors contributed equally to this work.
1
(a) A. Bassindale, P. P. Gaspar, Frontiers of Organosilicon
Chemistry; Royal Society of Chemistry: 1991; (b) G. L. Larson,
Advances in Silicon Chemistry; JAI Press: 1996; (c) N. Auner, J.
Weis, Organosilicon Chemistry V; WileyꢀVCH Verlag GmbH: 2003
(a) T. Hiyama, Metal-catalyzed Cross-Coupling Reactions, Wileyꢀ
VCH, Weinheim, 1998, Chap. 4; (b) M. A. Brook, Silicon in
Organic, Organometallic, and Polymer Chemistry, Wiley, New
York, 2000; (c) S. E. Denmark, J. H. Liu, Angew. Chem. Int. Ed.
.
2
2010, 49, 2978; (d) Y. Nakao, T. Hiyama, Chem. Soc. Rev. 2011, 40
,
4893; (e) H. F. Sore, W. R. J. D. Galloway, D. R. Spring, Chem. Soc.
Rev. 2012 41, 1845; (f) H. Luo, Z. Zhang, H. Liu, H. Liu, Chin. J.
Org. Chem. 2015 35, 802; (g) S. E. Denmark, A. Ambrosi, Org.
Process Res. Dev. 2015 19, 982; (h) H. Luo, H. Liu, X. Chen, K.
Wang, X. Luo, K. Wang, Chem. Commun. 2017 53, 956.
(a) L. Li, Y. Zhang, L. Gao, Z. Song, Tetrahedron Lett. 2015
,
,
,
,
3
4
,
56
,
1466; (b) T. Komiyama, Y. Minami, T. Hiyama, ACS Catal. 2017
,
7
,
631.
(a) A. Leo, C. Hansch, D. Elkins, Chem. Rev. 1971, 71, 525; (b) F.
Leroux, P. Jeschke, M. Schlosser, Chem. Rev. 2005
,
105, 827; (c) M.
44, 214; (d) B.
Shimizu, T. Hiyama, Angew. Chem. Int. Ed. 2005
,
Menteau, S. Pazenok, J. P. Vors, F. R. Leroux, J. Fluorine Chem.
2010 131, 140; (e) G. Landelle, A. Panossian, F. R. Leroux, Curr.
Top. Med. Chem. 2014 14, 941.
For recent reviews on trifluoromethoxylation reactions, see (a) A.
Tlili, F. Toulgoat, T. Billard, Angew. Chem. Int. Ed. 2016 55, 11726;
(b) T. Besset, P. Jubault, X. Pannecoucke, T. Poisson, Org. Chem.
Front. 2016 , 1004. For selected examples for the synthesis of
trifluoromethoxylated compounds, see (a) K. Stanek, R. Koller, A.
Togni, J. Org. Chem. 2008 73, 7678; (b) R. Koller, K. Stanek, D.
Stolz, R. Aardoom, K. Niedermann, A. Togni, Angew. Chem. Int. Ed.
2009 48, 4332; (c) O. Marrec, T. Billard, J. Vors, S. Pazenok, B. R.
Langlois, Adv. Synth. Catal 2010 352, 2831; (d) O. Marrec, T.
,
,
Scheme 2. Mechanistic studies and proposed mechanism
5
,
Conclusions
,
3
In conclusion, we have developed a silverꢀmediated oxidative
functionalization of alkylsilanes. This strategy enables to access a
range of functionalized products directly, thus obviating the need to
develop new methodology for each specific C−Si transformation.
,
Furthermore,
a
first example of silverꢀmediated trifluoroꢀ
,
methoxylation of alkylsilanes was developed using trifluoromethyl
.
,
4 | J. Name., 2012, 00, 1-3
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Billard, J. Vors, S. Pazenok, B. R. Langlois, J. Fluorine Chem. 2010
131, 200; (e) C. Huang, T. Liang, S. Harada, E. Lee, T. Ritter, J. Am.
Chem. Soc. 2011 133 13308; (f) C. Zhang, D. A. Vicic,
Organometallics 2012 31, 7812; (g) K. N. Hojczyk, P. Feng, C.
Zhan, M. Y. Ngai, Angew. Chem. Int. Ed. 2014 53, 14559; (h) J.
Liu, C. Chen, L. Chu, Z. Chen, X. Xu, F. Qing, Angew. Chem. Int.
,
(p) S. Mukherjee, B. Maji, A. TlahuextꢀAca, F. Glorius, J. Am.
Chem. Soc. 2016 138, 16200; (q) L. J. C. B. Milandou, H. Carreyre,
,
,
,
S. Alazet, G. Greco, A. MartinꢀMingot, C. N. Loumpangou, J.
,
,
Ouamba, F. Bouazza, T. Billard, S. Thibaudeau, Angew. Chem. Int.
,
Ed. 2017, 56, 169; (r) Z. Zhang, Z. Sheng, W. Yu, G. Wu, R. Zhang,
W. Chu, Y. Zhang, J. Wang, Nat. Chem. 2017, 9, 970.
Ed. 2015
,
54, 11839; (i) J. Liu, X. Xu, F. Qing, Org. Lett. 2015
,
17
,
,
7
8
9
(a) A. A. Kolomeitsev, M. Vorobyev, H. Gillandt, Tetrahedron Lett.
5048; (j) C. Chen, P. Chen, G. Liu, J. Am. Chem. Soc. 2015
,
137
2008
(c) J. Sheng, J. Wu, Org. Biomol. Chem. 2014
Alazet, L. Zimmer, T. Billard, Chem. Eur. J. 2014
Arimori, M. Takada, N. Shibata, Org. Lett. 2015
Zeng, J. Hu, Org. Lett. 2016
J. Hu, J. Am. Chem. Soc. 2018
(a) A. G. Brook, J. Am. Chem. Soc. 1958
Acc. Chem. Res. 1974 , 77; (c) A. Riahi, J. Cossy,; J. P. Muzart,
Pete, Tetrahedron lett 1985 26, 839; (d) A. S. Guram, Synlett 1993
, 259; (e) C. Kaimakliotis, A. J. Fry, J. Org. Chem. 2003 68, 9893;
(f) A. B. III. Smith, C. M. Adams, Acc. Chem. Res. 2004 37, 365; (g)
,
49, 449; (b) J. Liu, L. Chu, F. Qing, Org. Lett. 2013
, 15, 894;
15648; (k) S. Chen, Y. Huang, X. Fang, H. Li, Z. Zhang, T. S. Andy
Hor, Z. Weng, Dalton Trans 2015 44, 19682; (l) A. Liang, S. Han,
Z. Liu, L. Wang, J. Li, D. Zou, Y. Wu, Y. Wu, Chem. Eur. J. 2016
22, 5102; (m) P. Feng, K. N. Lee, J. W. Lee, C. Zhan, M. Y. Ngai,
Chem. Sci. 2016 , 424; (n) G. Zha, J. Han, X. Hu, H. Qin, W. Fang,
C. Zhang, Chem. Commun. 2016 52, 7458; (o) M. Zhou, C, Ni, Z.
He, J. Hu, Org. Lett. 2016 18, 3754; (p) C. ChatalovaꢀSazepin, M.
Binayeva, M. Epifanov, W. Zhang, P. Foth, C. Amador, M. Jagdeo,
B. R. Boswell, G. M. Sammis, Org. Lett. 2016 18, 4570; (q) Q.
Zhang, A. T. Brusoe, V. Mascitti, K. D. Hesp, D. C. Blakemore, J. T.
Kohrt, J. F. Hartwig, Angew. Chem. Int. Ed. 2016 55, 9758; (r) J. N.
Brantley, A. V. Samant, F. D.Toste, ACS Cent. Sci 2016 , 341; (s)
S. Krishanmoorthy, S. D. Schnell, H. Dang, F. Fu, G. K. S. Prakash,
J. Fluorine Chem. 2017 203, 130; (t) W. Huang, X. Wan, Q. Shen,
Angew. Chem. Int. Ed. 2017 56, 11986; (u) E. Schmitt, S. Bouvet, B.
Pégot, A. Panossian, J. Vors, S. Pazenok, E. Magnier, F. R. Leroux,
Org. Lett. 2017 19, 4960. (v) J. W. Lee, D. N. Spiegowski, M. Y.
Ngai, Chem. Sci. 2017 , 6066; (w) C. Chen, Y. Luo, L. Fu, P.
Chen, Y. Lan, G. Liu, J. Am. Chem. Soc. 2018 140, 1207; (x) M.
Zhou, C. Ni, Y. Zeng, J. Hu, J. Am. Chem. Soc. 2018 140, 6801; (y)
W. Zheng, C. A. MoralesꢀRivera, J. W. Lee, P. Liu, M. Ngai, 10 M. Arimoto, H. Yamaguchi, E. Fujita, M. Ochiai, Y. Nagao,
Angew. Chem. Int. Ed. 2018, DOI: 10.1002/anie.201800598; (z) B. Tetrahedron lett 1987 28, 6289.
J. Jelier, P. F. Tripet, E. Pietrasiak, I. Franzoni, G. Jeschke, A. Togni, 11 (a) S. Guo, F. Cong, R. Guo, L. Wang, P. Tang, Nat. Chem. 2017
,
12, 7629; (d) S.
.
,
,
20, 8589; (e) S.
,
, 17, 1063; (f) Y.
,
18, 856; (g) M. Zhou, C. Ni, Y. Zeng,
140, 6801.
80, 1886; (b) A. G. Brook,
,
7
,
,
,
,
, 7
.
,
,
,
4
,
,
,
Y. Deng, Q. Liu, A. B. III. Smith, J. Am. Chem. Soc. 2017, 139,
.
,
2
9487.
(a) K. Tamao, J. Yoshida, M. Takahashi, H. Yamanoto, T. Kakui, H.
,
Matsumoto, A. Kurita, M. Kumada, J. Am. Chem. Soc. 1978
,
100
,
,
,
290; (b) K. Tamao, T. Kakui, M. Kumada, J. Am. Chem. Soc. 1978
100, 2268; (c) J. Yoshida, K. Tamao, Kumada, M. J. Am. Chem. Soc.
1980 102, 3269; (d) K. Tamao, J. Yoshida, H. Yamamoto, T. Kakui,
H. Matsumoto, M. Takahashi, A. Kurita, M. Murata, M. Kumada,
Organometallics 1982 , 355; (e) P. Xu, F. Wang, G. Fan, X. Xu, P.
Tang, Angew. Chem. Int. Ed. 2017 56, 1101.
,
,
,
8
,
, 1
,
,
.
,
, 9,
Angew. Chem. Int. Ed. 2018, DOI: 10.1002/anie.201806296.
546; (b) X. Jiang, Z. Deng, P. Tang, Angew. Chem. Int. Ed. 2018
, 57,
6
For recent reviews on trifluoromethylthiolation reactions, see (a) X.
292; (c) F. Cong, Y. Wei, P. Tang, Chem. Commun. 2018 54, 4473;
,
Shao, C. Xu, L. Lu, Q. Shen, Acc. Chem. Res. 2015
Xu, K. Matsuzaki, N. Shibata, Chem. Rev. 2015
Chachignon, D. Cahard, Chin. J. Chem. 2016
,
48, 1227; (b) X.
(d) H. Yang, F. Wang, X. Jiang, Y. Zhou, X. Xu, P. Tang, Angew.
Chem. Int. Ed. 2018, DOI: 10.1002/anie.201807144.
,
115, 731; (c) H.
,
34, 445. For selected 12 For selected reviews, see: (a) S. Bräse, K. Banert, Organic Azides:
examples for the synthesis of trifluoromethylthiolated compounds,
Synthesis and Applications. WileyꢀVCH, Weinheim, 2010; (b) S.
Bräse, C. Gil, K. Knepper, V. Zimmermann, Angew. Chem. Int. Ed.
2005 44, 5188.
see: (a) A. Ferry, T. Billard, B. R. Langlois, E. Bacqué, Angew.
Chem. Int. Ed. 2009
Buchwald, Angew. Chem. Int. Ed. 2011
A. Vicic, J. Am. Chem. Soc. 2012 134, 183; (d) L. D. Tran, I. Popov,
O. Daugulis, J. Am. Chem. Soc. 2012 134, 18237; (e) X. Shao, X.
Wang, T. Yang, L. Lu, Q. Shen, Angew. Chem. Int. Ed. 2013 52
3457; (f) T. Bootwicha, X. Liu, R. Pluta, I. Atodiresei, M. Rueping,
Angew. Chem. Int. Ed. 2013 52, 12856; (g) Y. Yang, A. Azuma, E.
Tokunaga, M. Yamasaki, M. Shiro, N. Shibata, J. Am. Chem. Soc.
2013 135, 8782; (h) E. V. Vinogradova, P. Müller, S. L. Buchwald,
Angew. Chem. Int. Ed. 2014 53, 3125; (i) G. Danoun, B.
Bayarmagnai, M. F. Gruenberg. L. J. Goossen, Chem. Sci. 2014
1312; (j) F. Yin, X. Wang, Org. Lett. 2014 16, 1128; (k) J. Liu, X.
Xu, Z. Chen, F. Qing, Angew. Chem. Int. Ed. 2015 54, 897; (l) G.
Yin, I. Kalvet, U. Englert, F. Schoenebeck, J. Am. Chem. Soc. 2015
137, 4164; (m) S. Guo, X. Zhang, P. Tang, Angew. Chem. Int. Ed.
2015 54, 4065; (n) H. Wu, Z. Xiao, J. Wu, Y. Guo, J. Xiao, C. Liu,
Q. Chen, Angew. Chem. Int. Ed. 2015 54, 4070; (o) X. Liu, R. An,
X. Zhang, J. Luo, X. Zhao, Angew. Chem. Int. Ed. 2016 54, 5846;
,
48, 8551; (b) G. Teverovskiy, D. S. Surry, S. L.
,
,
50, 7312; (c) C. Zhang, D.
,
,
,
,
,
,
,
, 5,
,
,
,
,
,
,
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Chemical Science
Page 6 of 6
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DOI: 10.1039/C8SC03730B
A general approach to the functionalization of aliphatic C-Si bonds in the presence of
silver salt and oxidant has been reported.