Organic Letters
Letter
2002, 58, 8669−8677. (b) Kattnig, E.; Albert, M. Counterion-
directed regioselective acetylation of octyl β-D-glucopyranoside. Org.
Lett. 2004, 6, 945−948. (c) Kawabata, T.; Muramatsu, W.; Nishio, T.;
Shibata, T.; Schedel, H. A catalytic one-step process for the chemo-
and regioselective acylation of monosaccharides. J. Am. Chem. Soc.
2007, 129, 12890−12895. (d) Yanagi, M.; Imayoshi, A.; Ueda, Y.;
Furuta, T.; Kawabata, T. Carboxylate anions accelerate pyrrolidino-
pyridine (PPy)-catalyzed acylation: Catalytic site-selective acylation of
a carbohydrate by in situ counteranion exchange. Org. Lett. 2017, 19,
3099−3102.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This research was partially supported by JSPS KAKENHI
Grant No. 16K18850 (N.S.) for Young Scientists (B),
19K07000 (N.S.) for Scientific Research (C), 17K08218
(K.M.) for Scientific Research (C), and Kitasato University
Research Grant for Young Researchers. We thank Dr. K. Nagai
and Ms. M. Sato at Kitasato University for instrumental
analyses.
(7) Sun, X.; Lee, H.; Lee, S.; Tan, K. L. Catalyst recognition of cis-
1,2-diols enables site-selective functionalization of complex molecules.
Nat. Chem. 2013, 5, 790−795.
(8) For a selected example of ammonium salt catalysis, see: Zhang,
X.; Ren, B.; Ge, J.; Pei, Z.; Dong, H. A green and convenient method
for regioselective mono and multiple benzoylation of diols and
polyols. Tetrahedron 2016, 72, 1005−1010.
(9) Mensah, E.; Camasso, N.; Kaplan, W.; Nagorny, P. Chiral
phosphoric acid directed regioselective acetalization of carbohydrate-
derived 1,2-diols. Angew. Chem., Int. Ed. 2013, 52, 12932−12936.
(10) Cramer, D. L.; Bera, S.; Studer, A. Exploring cooperative effects
in oxidative NHC catalysis: Regioselective acylation of carbohydrates.
Chem. - Eur. J. 2016, 22, 7403−7407.
REFERENCES
■
(1) For selected reviews, see: (a) Lawandi, J.; Rocheleau, S.;
Moitessier, N. Regioselective acylation, alkylation, silylation and
glycosylation of monosaccharides. Tetrahedron 2016, 72, 6283−6319.
(b) Shugrue, C. R.; Miller, S. J. Applications of nonenzymatic catalysts
to the alteration of natural products. Chem. Rev. 2017, 117, 11894−
11951. (c) Dimakos, V.; Taylor, M. S. Site-selective functionalization
of hydroxyl groups in carbohydrate derivatives. Chem. Rev. 2018, 118,
11457−11517.
(11) Xiao, G.; Cintron-Rosado, G. A.; Glazier, D. A.; Xi, B.; Liu, C.;
Liu, P.; Tang, W. Catalytic site-selective acylation of carbohydrates
directed by cation−n interaction. J. Am. Chem. Soc. 2017, 139, 4346−
4349.
(2) For selected examples of Sn catalysis, see: (a) Demizu, Y.; Kubo,
Y.; Miyoshi, H.; Maki, T.; Matsumura, Y.; Moriyama, N.; Onomura,
O. Regioselective protection of sugars catalyzed by dimethyltin
dichloride. Org. Lett. 2008, 10, 5075−5077. (b) Muramatsu, W.;
Tanigawa, S.; Takemoto, Y.; Yoshimatsu, H.; Onomura, O. Organo-
tin-catalyzed highly regioselective thiocarbonylation of nonprotected
carbohydrates and synthesis of deoxy carbohydrates in a minimum
number of steps. Chem. - Eur. J. 2012, 18, 4850−4853. (c) Muramatsu,
W. Catalytic and regioselective oxidation of carbohydrates to
synthesize keto-sugars under mild conditions. Org. Lett. 2014, 16,
4846−4849. (d) Xu, H.; Lu, Y.; Zhou, Y.; Ren, B.; Pei, Y.; Dong, H.;
Pei, Z. Regioselective benzylation of diols and polyols by catalytic
amounts of an organotin reagent. Adv. Synth. Catal. 2014, 356, 1735−
1740.
(12) For selected examples of peptide catalysis, see: (a) Sculimbrene,
B. R.; Morgan, A. J.; Miller, S. J. Enantiodivergence in small-molecule
catalysis of asymmetric phosphorylation: Concise total syntheses of
the enantiomeric D-myo-inositol-1-phosphate and D-myo-inositol-3-
phosphate. J. Am. Chem. Soc. 2002, 124, 11653−111656. (b) Griswold,
K. S.; Miller, S. J. A peptide-based catalyst approach to regioselective
functionalization of carbohydrates. Tetrahedron 2003, 59, 8869−8875.
(c) Han, S.; Miller, S. J. Asymmetric catalysis at a distance: Catalytic,
site-selective phosphorylation of teicoplanin. J. Am. Chem. Soc. 2013,
135, 12414−12421. (d) Pelletier, G.; Zwicker, A.; Allen, C. L.;
Schepartz, A.; Miller, S. J. Aqueous glycosylation of unprotected
sucrose employing glycosyl fluorides in the presence of calcium ion
and trimethylamine. J. Am. Chem. Soc. 2016, 138, 3175−3182.
(e) Huber, F.; Kirsch, S. F. Site-selective acylations with tailor-made
catalysts. Chem. - Eur. J. 2016, 22, 5914−5918.
(3) For selected examples of Cu catalysis, see: (a) Matsumura, Y.;
Maki, T.; Tsurumaki, K.; Onomura, O. Kinetic resolution of D,L-myo-
inositol derivatives catalyzed by chiral Cu(II) complex. Tetrahedron
Lett. 2004, 45, 9131−9134. (b) Allen, C. L.; Miller, S. J. Chiral
copper(II) complex-catalyzed reactions of partially protected
carbohydrates. Org. Lett. 2013, 15, 6178−6181. (c) Chen, I.-H.;
Kou, K. G. M.; Le, D. N.; Rathbun, C. M.; Dong, V. M. Recognition
and site-selective transformation of monosaccharides by using
copper(II) catalysis. Chem. - Eur. J. 2014, 20, 5013−5018.
(d) Shang, W.; Mou, Z.-D.; Tang, H.; Zhang, X.; Liu, J.; Fu, Z.;
Niu, D. Site-selective O-arylation of glycosides. Angew. Chem., Int. Ed.
2018, 57, 314−318.
(13) (a) Lee, D.; Taylor, M. S. Borinic acid-catalyzed regioselective
acylation of carbohydrate derivatives. J. Am. Chem. Soc. 2011, 133,
3724−3727. (b) Chan, L.; Taylor, M. S. Regioselective alkylation of
carbohydrate derivatives catalyzed by a diarylborinic acid derivative.
Org. Lett. 2011, 13, 3090−3093. (c) Gouliaras, C.; Lee, D.; Chan, L.;
Taylor, M. S. Regioselective activation of glycosyl acceptors by a
diarylborinic acid-derived catalyst. J. Am. Chem. Soc. 2011, 133,
13926−13929. (d) Lee, D.; Williamson, C. L.; Chan, L.; Taylor, M. S.
Regioselective, borinic acid-catalyzed monoacylation, sulfonylation
and alkylation of diols and carbohydrates: Expansion of substrate
scope and mechanistic studies. J. Am. Chem. Soc. 2012, 134, 8260−
8267. (e) Beale, T. M.; Taylor, M. S. Synthesis of cardiac glycoside
analogs by catalyst-controlled, regioselective glycosylation of digitoxin.
Org. Lett. 2013, 15, 1358−1361. (f) Beale, T. M.; Moon, P. J.; Taylor,
M. S. Organoboron-catalyzed regio- and stereoselective formation of
β-2-deoxyglycosidic linkages. Org. Lett. 2014, 16, 3604−3607.
(g) Dimakos, V.; Su, H. Y.; Garrett, G. E.; Taylor, M. S. Site-
selective and stereoselective C−H alkylations of carbohydrates via
combined diarylborinic acid and photoredox catalysis. J. Am. Chem.
Soc. 2019, 141, 5149−5153.
(4) For selected examples of Fe catalysis, see: (a) Ren, B.;
̈
Ramstrom, O.; Zhang, Q.; Ge, J.; Dong, H. An iron(III) catalyst with
unusually broad substrate scope in regioselective alkylation of diols
and polyols. Chem. - Eur. J. 2016, 22, 2481−2486. (b) Lv, J.; Luo, T.;
Zhang, Y.; Pei, Z.; Dong, H. Regio/site-selective benzoylation of
carbohydrates by catalytic amounts of FeCl3. ACS Omega 2018, 3,
17717−17723.
̈
(5) For selected examples of Pd catalysis, see: (a) Jager, M.;
Hartmann, M.; de Vries, J. G.; Minnaard, A. J. Catalytic regioselective
oxidation of glycosides. Angew. Chem., Int. Ed. 2013, 52, 7809−7812.
(b) Chung, K.; Waymouth, R. M. Selective catalytic oxidation of
unprotected carbohydrates. ACS Catal. 2016, 6, 4653−4659.
(c) Eisink, N. N. H. M.; Witte, M. D.; Minnaard, A. J. Regioselective
carbohydrate oxidations: A nuclear magnetic resonance (NMR) study
on selectivity, rate, and side-product formation. ACS Catal. 2017, 7,
1438−1445.
́
(14) (a) Dimitrijevic, E.; Taylor, M. S. 9-Hetero-10-boraanthracene-
derived borinic acid catalysts for regioselective activation of polyols.
Chem. Sci. 2013, 4, 3298−3303. (b) D’Angelo, K. A.; Taylor, M. S.
Borinic acid catalyzed stereo- and regioselective couplings of glycosyl
methanesulfonates. J. Am. Chem. Soc. 2016, 138, 11058−11066.
(c) Gorelik, D.; Lin, Y. C.; Briceno-Strocchia, A. I.; Taylor, M. S.
(6) For selected examples of achiral or chiral DMAP catalysis, see:
(a) Kurahashi, T.; Mizutani, T.; Yoshida, J. Functionalized DMAP
catalysts for regioselective acetylation of carbohydrates. Tetrahedron
E
Org. Lett. XXXX, XXX, XXX−XXX