- Chemoselective Homologation-Deoxygenation Strategy Enabling the Direct Conversion of Carbonyls into (n+1)-Halomethyl-Alkanes
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The sequential installation of a carbenoid and a hydride into a carbonyl, furnishing halomethyl alkyl derivatives, is reported. Despite the employment of carbenoids as nucleophiles in reactions with carbon-centered electrophiles, sp3-type alkyl halides remain elusive materials for selective one-carbon homologations. Our tactic levers on using carbonyls as starting materials and enables uniformly high yields and chemocontrol. The tactic is flexible and is not limited to carbenoids. Also, diverse carbanion-like species can act as nucleophiles, thus making it of general applicability.
- Citarella, Andrea,Holzer, Wolfgang,Ielo, Laura,Langer, Thierry,Miele, Margherita,Pace, Vittorio,Urban, Ernst,Zehl, Martin
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supporting information
p. 7629 - 7634
(2020/10/12)
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- Organocatalytic Chlorination of Alcohols by P(III)/P(V) Redox Cycling
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A catalytic system for the chlorination of alcohols under Appel conditions was developed. Benzotrichloride is used as a cheap and readily available chlorinating agent in combination with trioctylphosphane as the catalyst and phenylsilane as the terminal reductant. The reaction has several advantages over other variants of the Appel reaction, e.g., no additional solvent is required and the phosphane reagent is used only in catalytic amounts. In total, 27 different primary, secondary, and tertiary alkyl chlorides were synthesized in yields up to 95%. Under optimized conditions, it was also possible to convert epoxides and an oxetane to the dichlorinated products.
- Longwitz, Lars,Jopp, Stefan,Werner, Thomas
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p. 7863 - 7870
(2019/06/27)
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- Triphosgene-amine base promoted chlorination of unactivated aliphatic alcohols
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Unactivated α-branched primary and secondary aliphatic alcohols have been successfully transformed into their corresponding alkyl chlorides in high yields upon treatment with a mixture of triphosgene and pyridine in dichloromethane at reflux. These mild chlorination conditions are high yielding, stereospecific, and well tolerated by numerous sensitive functionalities. Furthermore, no nuisance waste products are generated in the course of the reactions.
- Villalpando, Andres,Ayala, Caitlan E.,Watson, Christopher B.,Kartika, Rendy
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p. 3989 - 3996
(2013/06/04)
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- The 1,2-diphenylethyl cation via carbene fragmentation
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2,2-Diphenylethoxychlorocarbene fragments with kfrag=2.1×106 s-1 in MeCN, largely with 1,2-phenyl migration and the formation of rearranged products. Related chemistry is observed for the 2,2-diphenylethyldiazonium cation.
- Moss, Robert A,Ma, Yan
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p. 6045 - 6048
(2007/10/03)
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- The conversion of alcohols to halides using a filterable phosphine source
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The conversion of primary and secondary alcohols to chlorides and bromides using 1,2-bis(diphenylphosphino)ethane (diphos) is described. Use of this reagent in lieu of the typical triphenylphosphine-carbontetrahalide complex provides a facile means of purifying the desired halide from the phosphine-oxide byproduct.
- Pollastri, Michael P.,Sagal, John F.,Chang, George
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p. 2459 - 2460
(2007/10/03)
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- An Electron Spin Resonance Investigation of β-Substituted 1,1-Diphenylethyl Radicals
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A large number of β-substituted 1,1-diphenylethyl derivatives Ph2C.CH2MRn have been generated by addition of .MRn radicals to 1,1-diphenylethylene.The magnitude of the β-proton hyperfine splitting constants toge
- Leardini, Rino,Tundo, Antonio,Zanardi, Giuseppe,Pedulli, Gian Franco
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p. 285 - 290
(2007/10/02)
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