Pd(II)-catalyzed acetal/ketal hydrolysis/exchange reactions

Lipshutz, Bruce H.; Pollart, Daniel J.; Monforte, Joseph; Kotsuki, Hiyoshizo

doi:10.1016/s0040-4039(00)89114-5

Cited by 184 publications

(80 citation statements)

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“…For example, treatment of 3-butenyl heptyl ketone (32) with a catalytic amount of 2 in the presence of Me 3 SiCl and CuCl 2 formed 2-hexylcyclohexanone (33) [27] In hindsight, the palladium-catalyzed hydrolysis of Me 3 SiCl was not surprising, as 2 also catalyzes the hydrolysis of tert-butyldimethyl silyl ethers. [28] Similar results were obtained from 1 H NMR analysis of the reaction of benzyl 3-butenyl ketone (18) with Me 3 SiCl and 2.…”

Section: Limitations Of the Silane-mediated Protocolsupporting

confidence: 73%

Palladium‐Catalyzed Intramolecular Hydroalkylation of Alkenyl‐ β‐Keto Esters, α‐Aryl Ketones, and Alkyl Ketones in the Presence of Me₃SiCl or HCl

Han¹,

Wang²,

Pei³

et al. 2004

Chemistry A European J

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Reaction of 3-butenyl beta-keto esters or 3-butenyl alpha-aryl ketones with a catalytic amount of [PdCl2(CH3CN)2] (2) and a stoichiometric amount of Me3SiCl or Me3SiCl/CuCl2 in dioxane at 25-70 degrees C formed 2-substituted cyclohexanones in good yield with high regioselectivity. This protocol tolerated a number of ester and aryl groups and tolerated substitution at the allylic, enolic, and cis and trans terminal olefinic positions. In situ NMR experiments indicated that the chlorosilane was not directly involved in palladium-catalyzed hydroalkylation, but rather served as a source of HCl, which presumably catalyzes enolization of the ketone. Identification of HCl as the active promoter of palladium-catalyzed hydroalkylation led to the development of an effective protocol for the hydroalkylation of alkyl 3-butenyl ketones that employed sub-stoichiometric amounts of 2, HCl, and CuCl2 in a sealed tube at 70 degrees C.

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Section: Limitations Of the Silane-mediated Protocolsupporting

confidence: 73%

Palladium‐Catalyzed Intramolecular Hydroalkylation of Alkenyl‐ β‐Keto Esters, α‐Aryl Ketones, and Alkyl Ketones in the Presence of Me₃SiCl or HCl

Han¹,

Wang²,

Pei³

et al. 2004

Chemistry A European J

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“…Coupling of 16b,17a-diol 11 b with disaccharide imidate 12 [5] in the presence of TMSOTf (0.1 equiv) and 4-MS gave glycoside 13 b in a satisfactory yield (64 %), without production of a significant amount of lactone 14. Finally, deprotection of the silyl groups by treatment with [PdCl 2 (MeCN) 2 ] [17] afforded the desired product 1 in 86 % yield. The congeners 2 and 3, which have a shorter or a longer side chain than 1, were similarly prepared from 8 a and 8 c, respectively.…”

Section: Methodsmentioning

confidence: 99%

23‐Oxa‐Analogues of OSW‐1: Efficient Synthesis and Extremely Potent Antitumor Activity

Shi¹,

Wu²,

Yu³

et al. 2004

Angew Chem Int Ed

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“…Finally, the hydroazulenes 4a and 4b could be generated by palladium-catalyzed acetal cleavage [20] and subsequent aldol condensations under basic conditions [21,22] (Scheme 3). For 4b, an alternative combination of PPTSinduced deblocking [23] of 14 and aldol condensation without purification of diketone 16 turned out to be more productive.…”

Section: Resultsmentioning

confidence: 99%

Enantioselective Synthesis of the Hydroazulene Core of 3α‐Hydroxy‐15‐rippertene

Kreuzer

Metz

2008

Eur J Org Chem

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As part of a project directed toward the total synthesis of the tetracyclic diterpene 3α‐hydroxy‐15‐rippertene, a constituent of the defense secretion of higher termites, a fast access to two advanced hydroazulene key intermediates has been achieved by starting from (–)‐isopulegol. A regio‐ and diastereoselective formal hydromethallylation and a regioselective ring expansion served as the key steps in the formation of the seven‐membered ring. Completion of the bicyclic title compounds was then achieved by cyclopentene annulation through diastereoselective conjugate addition of organocuprates and subsequent intramolecular aldol condensations.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Pd(II)-catalyzed acetal/ketal hydrolysis/exchange reactions

Cited by 184 publications

References 4 publications

Palladium‐Catalyzed Intramolecular Hydroalkylation of Alkenyl‐ β‐Keto Esters, α‐Aryl Ketones, and Alkyl Ketones in the Presence of Me₃SiCl or HCl

Palladium‐Catalyzed Intramolecular Hydroalkylation of Alkenyl‐ β‐Keto Esters, α‐Aryl Ketones, and Alkyl Ketones in the Presence of Me₃SiCl or HCl

23‐Oxa‐Analogues of OSW‐1: Efficient Synthesis and Extremely Potent Antitumor Activity

Enantioselective Synthesis of the Hydroazulene Core of 3α‐Hydroxy‐15‐rippertene

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Pd(II)-catalyzed acetal/ketal hydrolysis/exchange reactions

Cited by 184 publications

References 4 publications

Palladium‐Catalyzed Intramolecular Hydroalkylation of Alkenyl‐ β‐Keto Esters, α‐Aryl Ketones, and Alkyl Ketones in the Presence of Me3SiCl or HCl

Palladium‐Catalyzed Intramolecular Hydroalkylation of Alkenyl‐ β‐Keto Esters, α‐Aryl Ketones, and Alkyl Ketones in the Presence of Me3SiCl or HCl

23‐Oxa‐Analogues of OSW‐1: Efficient Synthesis and Extremely Potent Antitumor Activity

Enantioselective Synthesis of the Hydroazulene Core of 3α‐Hydroxy‐15‐rippertene

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Palladium‐Catalyzed Intramolecular Hydroalkylation of Alkenyl‐ β‐Keto Esters, α‐Aryl Ketones, and Alkyl Ketones in the Presence of Me₃SiCl or HCl

Palladium‐Catalyzed Intramolecular Hydroalkylation of Alkenyl‐ β‐Keto Esters, α‐Aryl Ketones, and Alkyl Ketones in the Presence of Me₃SiCl or HCl