Murugan Subaramanian et al.
Etherification of Unactivated C-H Bonds Tetrahedron
substrate scope (aliphatic primary and secondary, and
aromatic alcohols) were efficiently converted into dialk-
oxymethanes in moderate to good yields (up to 89%)
under benign conditions. Solvent-free conditions, mod-
erate temperature, shorter reaction times, and economic
viability of the catalyst are the key features of the present
protocol.
Lett. 56 15 references cited therein
4
. (a) Burger J, Siegert M, Strçfer E and Hasse H 2010
Poly(Oxymethylene) Dimethyl Ethers as Components of
Tailored Diesel Fuel: Properties, Synthesis and Purifi-
cation Concepts Fuel 89 3315; (b) Burger J, Strçfer
E and Hasse H 2013 Production Process for Diesel
Fuel Components Poly(Oxymethylene) Dimethyl Ethers
from Methane-based Products by Hierarchical Opti-
mization with Varying Model Depth Chem. Eng. Res.
Des. 91 2648
5. Agui H, Mitani T, Izawa A, Komatsu T and Nak-
agome T 1977 Studies on Quinoline Derivatives and
Related Compounds. 5. Synthesis and Antimicro-
bial Activity of Novel 1-Alkoxy-1,4-dihydro-4-oxo-3-
quinolinecarboxylic Acids J. Med. Chem. 20 791
Supplementary Information (SI)
Full characterization details, copies of NMR ( H and 13
1
C
NMR) spectra, HRMS data for all the compounds are pre-
6
. Paudler W W, Kerley G I and McKay J 1963 The Alka-
loids of Cephalotaxus Drupacea and Cephalotaxus For-
tune J. Org. Chem. 28 2194; (b) Gouthami P, Chegondi
R and Chandrasekhar S 2016 Formal Total Synthesis of
Acknowledgements
This research was supported by the SERB (SB/FT/CS-
065/2013). MS and AB thank UGC, India for the research
(
± )-Cephalotaxine and Congeners via Aryne Insertion
fellowships. BLVP acknowledges the Council of Scien-
tific and Industrial Research, India for the financial support
through the project CSC0134.
Reaction Org. Lett. 18 2044
7. Kulkarni M G, Davawala S I, Doke A K and Doke A V
2003 A Novel Synthesis of Diallyloxymethanes Indian
J. Chem. 42B 2121
8
. Hopkins A L, Ren J, Esnouf R M, Willcox B E, Jones
EY, Ross C, Miyasaka T, Walker R T, Tanaka H, Stam-
mers D K and Stuart D I 1996 Complexes of HIV-1
ReverseTranscriptasewithInhibitors of theHEPTSeries
Reveal Conformational Changes Relevant to the Design
of Potent Non-Nucleoside Inhibitors J. Med. Chem. 39
1589
References
1
. (a) Kubo K, Kohara Y, Imamiya E, Sugiura Y, Inada Y,
Furukawa Y, Nishikawa K and Naka T 1993 Nonpep-
tide Angiotensin II Receptor Antagonists. Synthesis and
Biological Activity of Benzimidazolecarboxylic acids J.
Med. Chem. 36 2182; (b) Ohkawa S, Fukatsu K, Miki S,
Hashimoto T, Sakamoto J, Doi T, Nagai Y and Aono T
9. Loksha Y M, Pedersen E B, Loddo R, Sanna G, Collu
G, Giliberti G and Colla P L Synthesis of Novel Fluoro
Analogues of MKC442 as Microbicides Med. Chem. 57
5169
1
997 5-Aminocoumarans: Dual Inhibitors of Lipid Per-
oxidation and Dopamine Release with Protective Effects
Against Central Nervous System Trauma and Ischemia 10. Wang Z, Bennett E M, Wilson D J, Salomon C and Vince
J. Med. Chem. 40 559; (c) Esteki M and Khayamian T
008 Mechanistic-based Descriptors for QSAR Study of
Psychotropic Drug Toxicity Chem. Biol. Drug Des. 72
09
. (a) March J 1992 In Advanced Organic Chemistry,
Reactions, Mechanisms and Structure (New York: John
Wiley) p. 386; (b) Mandal S, Mandal S, Ghosh S K, Sar
R 2007 Rationally Designed Dual Inhibitors of HIV
Reverse Transcriptase and Integrase J. Med. Chem. 50
3416
2
4
11. Tang J, Maddali K, Metifiot M, Sham Y Y, Vince R,
Pommier Y and Wang Z 2011 3-Hydroxypyrimidine-
2,4-diones as an Inhibitor Scaffold of HIV Integrase J.
Med. Chem. 54 2282
2
P, Ghosh A, Saha R and Saha B 2016 A Review on the 12. Szmigielski
R
and Danikiewicz
W
2003 N-
Advancement of Ether Synthesis from Organic Solvent
to Water RSC Adv. 6 69605
. (a) Hartwig J F 1998 Carbon-Heteroatom Bond-Forming
AlkoxymethylationofSecondaryAmides, Sulfonamides
and Phosphamides Using Dialkoxymethanes in the Pres-
ence of Lewis Acids Synlett 372
3
Reductive Eliminations of Amines, Ethers, and Sulfides 13. Ledneczki I, Agócs P M and Molnár A 2003 N-
Acc. Chem. Res. 31 852; (b) Hartwig J F 1998 Tran-
sition Metal Catalyzed Synthesis of Arylamines and
Alkoxymethylation of Carboxamides Catalyzed by
Brønsted Acids Synlett 2255
Aryl Ethers from Aryl Halides and Triflates: Scope and 14. (a) Bal B S and Pinnick H W 1979 Convenient Conver-
Mechanism Angew. Chem. Int. Ed. 37 2046; (c) Ley S
V and Thomas A W 2003 Modern Synthetic Methods
for Copper-Mediated C(aryl)[bond]O, C(aryl)[bond]N,
and C(aryl)[bond]S Bond Formation Angew. Chem. Int.
Ed. 42 5400; (d) Shintou T and Mukaiyama T 2004
Efficient Methods for the Preparation of Alkyl-Aryl and
Symmetrical or Unsymmetrical Dialkyl Ethers between
Alcohols and Phenols or Two Alcohols by Oxidation-
Reduction Condensation J. Am. Chem. Soc. 126 7359;
sion of Alcohols into Formaldehyde Acetals or Ethers
J. Org. Chem. 44 3727; (b) Barot B C and Pinnick H
W 1981 Preparation of Formaldehyde and Acetalde-
hyde Acetals J. Org. Chem. 46 2981; (c) Cornelius
A and Lazlo P 1982 Clay-Supported Reagents; II.
Quaternary Ammonium-Exchanged Montmorillonite as
Catalyst in the Phase-Transfer Preparation of Symmetri-
cal Formaldehyde Acetals Synthesis 162; (d) Deshmukh
A R A S, Gumaste V K and Bhawal B M 1995 Mont-
morillonite, an Efficient Catalyst for the Preparation of
(e) Liu B and Shi B.-F 2015 Transition-Metal-Catalyzed