Asymmetric cyclization–carbonylation of 2-alkyl-2-propargylcyclohexane-1,3-diones: facile access to optically active hydrindanes

Kusakabe, Taichi; Kato, Kanefusa; Takaishi, Satoshi; Yamamura, Shigeo; Mochida, Tomoyuki; Akita, Hiroyuki; Peganova, T. A.; Vologdin, Nikolai V.; Gusev, O. B.

doi:10.1016/j.tet.2007.10.106

Cited by 39 publications

(15 citation statements)

References 54 publications

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“…33,34 The synthesis and characterization data of the ( R,R )-4- t -Bu-Ph-Box, ( R,R )-4-MeO-Ph-Box and ( S,S )-4-CF 3 -Ph-Box ligands have been reported. 35,36 …”

Section: Methodsmentioning

confidence: 99%

Mechanistic Analysis and Optimization of the Copper-Catalyzed Enantioselective Intramolecular Alkene Aminooxygenation

2012

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The catalytic asymmetric aminooxygenation of alkenes provides an efficient and straightforward approach to prepare chiral vicinal amino alcohols. We have reported a copper(II)-catalyzed enantioselective intramolecular alkene aminooxygenation, using (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) as the oxygen source, which results in the synthesis of chiral indolines and pyrrolidines. Herein we disclose that kinetics studies indicate the reaction is first order both in substrate and the [Cu(R,R)-Ph-bis(oxazoline)]OTf2 catalyst, and zero order in TEMPO. Furthermore, kinetic isotope effect studies support that the cis aminocupration step, the addition of N-Cu across the alkene, is the rate-limiting step. Subsequent formation of a carbon radical intermediate, and direct carbon radical trapping with TEMPO is the indicated mechanism for the C-O bond formation as suggested by a deuterium labeling experiment. A ligand screen revealed that C(4)-phenyl substitution on the bis(oxazoline) is optimal for high asymmetric induction. The size of the substrate’s N-sulfonyl group also influences the enantioselectivity of the reaction. The preparative scale catalytic aminooxygenation reaction (gram scale) was demonstrated and an unexpected dependence on reaction temperature was uncovered on the larger scale reaction.

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“…33,34 The synthesis and characterization data of the ( R,R )-4- t -Bu-Ph-Box, ( R,R )-4-MeO-Ph-Box and ( S,S )-4-CF 3 -Ph-Box ligands have been reported. 35,36 …”

Section: Methodsmentioning

confidence: 99%

Mechanistic Analysis and Optimization of the Copper-Catalyzed Enantioselective Intramolecular Alkene Aminooxygenation

2012

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“…The cyclic ketals can be easily converted into 2-cyclopentenones, which are useful intermediates of natural products [49]. Later, the same group extended this method to the cyclocarbonylation of propargylic acetates [50], propargylic esters [51], and 2-propargyl-1,3-dione [52,53]. Furthermore, using chiral bisoxazoline ligands, they realized the asymmetric cyclization-carbonylation of 2-alkyl-2-propargylcyclohexane-1,3-diones successfully.…”

Section: Scheme 4 Synthesis Of Four-membered Lactams Via Oxidative Camentioning

confidence: 99%

Synthesis of Functionalized Heterocycles via Oxidative Carbonylation

Xing

2015

Topics in Heterocyclic Chemistry

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With the assistance of a proper oxidant, carbonylation of two nucleophiles can take place directly in carbonylation conditions, which is defined as oxidative carbonylation. This process starts with the reaction of nucleophiles with the metal catalyst in oxidation state (M (n + 2) ), followed by insertion of CO and subsequent reductive elimination, providing the carbonylated products and the metal catalyst in reduction state (M (n) ). The oxidant could reoxidize M (n) to M (n + 2) to promote the catalytic cycle. Oxidative carbonylation avoids the difficult oxidative addition of R-X to metal catalyst, so this kind of carbonylation could proceed in mild conditions. What's more is that oxidative carbonylation doesn't need prefunctionalization of substrates. So, it's no wonder that considerable attention has been drawn to construct important carbonylated compounds through oxidative carbonylation. Particularly, much progress in synthesis of carbonylated heterocycles via oxidative carbonylation has been achieved in the past decades. Here, we summarized the main achievements in this area from 1982 to the beginning of 2015.

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“…"Auto-tandem catalysis" leading to 5-(carbamoylmethylene)oxazolidinin-2-ones 29. [23] The same group has recently reported the one-pot synthesis of 4-methoxy-6-(3-phenylpropyl)-5,6-dihydropyran-2one (35, dihydrokawain, an important natural product, Scheme 23) by oxidative alkoxy-cyclocarbonylation of 7phenylhept-1-yn-4-ol (34). [22] An enantioselective version of this kind of reactivity has been applied to the synthesis of nonracemic bicyclic β-alkoxyacrylates 33 (Scheme 22) starting from 2-alkyl-2-propargylcyclohexane-1,3-diones 32 in the presence of Pd-(TFA) 2 /2,2Ј-isopropylidene-bis[(4R)-4-(3,4-dimethoxyphenyl)-2-oxaxine].…”

Section: Oxidative Carbonylation Of Acetylenic Substrates Leading To mentioning

confidence: 99%

“…[24] Propargyl alcohols were converted into the corresponding five-membered lactones in a similar way. [23] Scheme 23. Synthesis of cyclic orthoesters 31 by (MeCN) 2 PdCl 2 -catalysed oxidative heterocyclization/alkoxycarbonylation of propargylates 30.…”

Section: Oxidative Carbonylation Of Acetylenic Substrates Leading To mentioning

confidence: 99%

Oxidative Carbonylation as a Powerful Tool for the Direct Synthesis of Carbonylated Heterocycles

2012

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Asymmetric cyclization–carbonylation of 2-alkyl-2-propargylcyclohexane-1,3-diones: facile access to optically active hydrindanes

Cited by 39 publications

References 54 publications

Mechanistic Analysis and Optimization of the Copper-Catalyzed Enantioselective Intramolecular Alkene Aminooxygenation

Mechanistic Analysis and Optimization of the Copper-Catalyzed Enantioselective Intramolecular Alkene Aminooxygenation

Synthesis of Functionalized Heterocycles via Oxidative Carbonylation

Oxidative Carbonylation as a Powerful Tool for the Direct Synthesis of Carbonylated Heterocycles

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