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ACS Catalysis
(
7) Selected examples: (a) Denton, R. M.; An, J.; Adeniran, B.
J. J.; Staskiewicz, S.; Spaller, M.; Martin, S. F. 4-
Dodecylbenzenesulfonylazide. Org. Synth. 1996, 73, 144. (c)
Steven M. Weinreb, S. M.; Chase, C. E.; Wipf, P.; Venkatraman, S.;
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Phosphine oxide-catalysed chlorination reactions of alcohols
under Appel conditions. Chem. Commun. 2010, 46, 3025-3027. (b)
Denton, R. M.; An, J.; Adeniran, B.; Blake, A. J.; Lewis, W.; Poulton,
A. M. Catalytic Phosphorus(V)-Mediated Nucleophilic
Heintzelman,
G.
R.;
Boeckman,
R.
K.
Jr.
2-
Trimethylsilylethanesulfonyl chloride. Org. Synth. 1998, 75, 161.
(d) Iserloh, U.; Oderaotoshi, Y.; Kanemasa, S.; Curran, D. P.;
Gordon, R. S.; Holmes, A. B. Synthesis of (R,R)-4,6-
dibenzofurandiyl-2,2´-bis(4.phenyloxazoline) (DBFOX/Ph) – A
novel tridentate ligand. Org. Synth. 2003, 80, 46. (e) Anderson, C.
E.; Overman, L. E.; Richards, C. J.; Watson, M. P.; White, N.;
Substitution Reactions: Development of
a Catalytic Appel
Reaction. J. Org. Chem. 2011, 76, 6749-6767. (c) Denton, R. M.;
Tang, X.; Przeslak, A. Catalysis of Phosphorus(V)-Mediated
Transformations: Dichlorination Reactions of Epoxides Under
Appel Conditions. Org. Lett. 2010, 10, 4678-4681. (d) Beddoe, R.
H.; Andrews, K. G.; Magné, V.; Cuthbertson, J. D.; Saska, J.;
Shannon-Little, A. L.; Shanahan, S. E.; Sneddon, H. F.; Denton, R.
M. Redox-neutral organocatalytic Mitsunobu reactions. Science
5
Bolger, J.; Miller, M. J. Preparation of ( -(S)-2-(4-
4
methylethyl)oxazolinylcyclopentadienyl)-( -
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
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3
4
5
6
7
8
9
0
1
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3
4
5
6
7
8
9
0
1
2
3
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5
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7
8
9
0
tetraphenylcyclobutadien)cobalt Org. Synth. 2007, 84, 139. (f)
Kuethe, J. T.; Beutner, G. L.; Denmark, S. E.; Muhuhim, J. M.
Synthesis of 2-arylindole-4-carboxylic amides: [2-(fluorophenyl)-
1-H-indol-4-yl]-1-pyrrolidinylmethanone. Org. Synth. 2009, 86,
92. (g) Yang, Q.; Ulysse, L. G.; McLaws, M. D.; Keefe, D. K.; Guzzo,
P. R.; Haney., B. P.; Cosbie., A. S.; Faul., M. M. Preparation of
Tetrahydroisoquinoline-3-ones Via Cyclization of Phenyl
Acetamides Using Eaton's Reagent. Org. Synth. 2012, 89, 44.
(13) For chlorinations of alcohols using Vilsmeier Haack type
reagents see: (a) Hepburn, D. R.; Hudson, H. R. Factors in the
formation of isomerically and optically pure alkyl halides. Part XI.
Vilsmeier reagents for the replacement of a hydroxy-group by
chlorine or bromine. J. Chem. Soc. Perkin Trans. I 1976, 754-757.
(b) Yoshihara, M.; Eda, T.; Sakai, K.; Maeshima, T. Conversion of
Alcohols to Alkyl Halides using Iminium Salts. Synthesis 1980,
746-748. (c) De Luca, L.; Giacomelli, G.; Porcheddu, A. An
Efficient Route to Alkyl Chlorides from Alcohols Using the
Complex TCT/DMF. Org. Lett. 2002, 4, 553-555. (d) Dubey, A.;
Upadhyay, A. K.; Kumar, P. Pivaloyl chloride/DMF: a new reagent
for conversion of alcohols to chlorides. Tetrahedron Lett. 2010, 51,
744-746. (e) Dai, C.; Narayanam, J. M. R.; Stephenson, C. R. J.
Visible-light-mediated conversion of alcohols to halides. Nature
Chem. 2011, 3, 140-145. (f) see also (4b) and (11f).
(14) Reviews on Lewis base catalysis: (a) Vedejs, E.; Dennmark,
S. E. Lewis Base Catalysis in Organic Synthesis, Wiley-VCH,
Weinheim, 2016, 1. (b) Denmark, S. E.; Beutner, G. L.
Lewis-Base-Katalyse in der organischen Synthese. Angew. Chem.
2008, 120, 1584-1663; Lewis Base Catalysis in Organic Synthesis.
Angew. Chem. Int. Ed. 2008, 47, 1560-1638. (c) Beutner, G. L.;
Denmark, S. E. Lewis-Base-Katalyse der gerichteten
Mukaiyama-Aldolreaktion: 40ꢀJahre Inspiration und Fortschritt.
Angew. Chem. 2013, 125, 9256-9266; Lewis base catalysis of the
Mukaiyama directed aldol reaction: 40 years of inspiration and
advances. Angew. Chem. Int. Ed. 2013, 52, 9086-9096. Examples of
Lewis base catalyzed reactions: (d) Denmark, S. E.; Burk, M. T.
Lewis base catalysis of bromo- and iodolactonization, and
cycloetherification. PNAS, 2010, 107, 20655-20660. (e) Matviitsuk,
A.; Denmark, S. E. Enantio- and Diastereoselective, Lewis Base
Catalyzed, Cascade Sulfenoacetalization of Alkenyl Aldehydes.
Angew. Chem. 2019, 131, 12616-12620; Enantio- and
2
019, 365, 910-914.
8) (a) Vanos, C. M.; Lambert, T. H. Development of a Catalytic
Platform for Nucleophilic Substitution:
(
Cyclopropenone-Catalyzed Chlorodehydration of Alcohols.
Angew. Chem. Int. Ed. 2011, 50, 12222-12226; Angew. Chem. 2011,
1
23, 12430-12434. (b) Nacsa, E. D.; Lambert, T. H. Cyclopropenone
Catalyzed Substitution of Alcohols with Mesylate Ion. Org. Lett.
013, 15, 38-41. (c) Stach, T.; Dräger, J.; Huy, P. H. Nucleophilic
Substitutions of Alcohols in High Catalytic Efficiency. Org. Lett.
2
2
018, 20, 2980-2983.
(9) (a) Nguyen, T. V.; Bekensir, A. Aromatic Cation Activation:
Nucleophilic Substitution of Alcohols and Carboxylic Acids. Org.
Lett. 2014, 16, 1720-1723. (b) Nguyen, T. V.; Lyons, D. J. M. A novel
aromatic carbocation-based coupling reagent for esterification
and amidation reactions. Chem. Commun. 2015, 51, 3131-3134.
(
10) The catalytic effect of the well-known Lewis base para-N,N-
dimethylaminopyridine on acylation reactions was discovered
later: (a) Steglich, W.; Höfle, G. 4-Dimethylamino-pyridin, ein
hochwirksamer Acylierungskatalysator Angew. Chem. 1969, 81,
1
001; N,N-Dimethyl-4-pyridinamine, a Very Effective Acylation
Catalyst. Angew. Chem. Int. Ed. Engl. 1969, 8, 981. (b) Höfle, G.;
Steglich, W. 4-Dialkylaminopyridines as Acylation Catalysts; III1.
Acylation of Sterically Hindered Alcohols. Synthesis 1972, 619-621;
for recent seminal mechanistic investigations into Lewis acid
catalyzed alcohol activations see: (c) Montalvo-Acosta, J. J.;
Dryzhakov, M.; Richmond, E.; Cecchini, M.; Moran, J. A
Supramolecular Model for the Co-Catalytic Role of Nitro
Compounds in Brønsted Acid Catalyzed Reactions. Chem. Eur. J.
2
020, 26, 10976-10980; (d) Zhang, S.; Leboeuf, D.; Moran,
Brønsted Acid and H-Bond Activation in Boronic Acid Catalysis.
J. Chem. Eur. J. 2020, 26, 9883-98888.
(
11) Reviews on Vilsmeier Haack reagent: (a) Marson, C. M.
Reactions of carbonyl compounds with (monohalo)
methyleniminium salts (vilsmeier reagents). Tetrahedron 1992,
4
8, 3659-3726. (b) Jones, G.; Stanforth, S. P. Vilsmeier Reaction of
Fully Conjugated Carbocycles and Heterocycles. Org. React. 1997,
9, 1. (c) Reichardt, C. Vilsmeier–Haack–Arnold formylations of
aliphatic substrates with
4
N-chloromethylene-N,N-dimethylammonium salts. J. Prakt.
Chem. 1999, 341, 609-615. (d) Jones, G.; Stanforth, S. P. Vilsmeier
Reaction. 2. Reactions with Compounds Other Than Fully
Conjugated Carbocycles and Heterocycles. Org. React. 2000, 56,
Diastereoselective,
Lewis
Base
Catalyzed,
Cascade
Sulfenoacetalization of Alkenyl Aldehydes. Angew. Chem. Int. Ed.
2019, 58, 12486-12490. (g) Wang, Z.; Cheng, M.; Wu, P.; Wei, S.;
Sun, J. L-Piperazine-2-carboxylic Acid Derived N-Formamide as a
Highly Enantioselective Lewis Basic Catalyst for Hydrosilylation
of N-Aryl Imines with an Unprecedented Substrate Profile. Org.
Lett. 2006, 8, 3045-3048. (h) Lettan, R. B.; Scheidt, K. A. Lewis
Base-Catalyzed Additions of Alkynes Using Trialkoxysilylalkynes.
Org. Lett. 2005, 7, 3227-3230. (i) Maddox, S. M.; Nalbandian, C. J.;
Smith, D. E.; Gustafson, J. L. A Practical Lewis Base Catalyzed
Electrophilic Chlorination of Arenes and Heterocycles. Org. Lett.
2015, 17, 1042-1045. (j) Liu, D.; Ding, W.; Zhou, Q.-Q.; Wei, Y.; Lu,
L.-Q.; Xiao, W.-J. Catalyst-Controlled Regioselective Acylation of
β-Ketoesters with α-Diazo Ketones Induced by Visible Light. Org.
3
55. (e) Lellouche, J.-P.; Kotlyar, V. Vilsmeier-Haack Reagents.
Novel Electrophiles for the One-Step Formylation of O-Silylated
Ethers to O-Formates. Synlett, 2004, 564-571. (g) Zhang, N.; Dong,
D. in Science of Synthesis, Vol. 2; Van Leeuwen, P. W. N. M., Ed.;
Thieme: Stuttgart, 2014, 333. For Preparation of 9g with phthaloyl
chloride see: (f) Kimura, Y.; Matsuura, D.; Hanawa, T.; Kobayashi,
Y. New preparation method for Vilsmeier reagent and related
imidoyl chlorides. Tetrahedron Lett. 2012, 53, 1116-1118.
(
12) Recent examples: (a) Wang, X.; de Silva, S. O.; Reed, J. N.;
Billadeau, R.; Griffen, E. J.; Chan, A.; Snieckus, V.; Limberakis, C.;
Martin, S. F. 7-Methoxyphthalide. Org. Synth. 1995, 72, 163. (b)
Hazen, G. G.; Bollinger, F. W.; Roberts, F. E.; Russ, W. K.; Seman,
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