The Chemistry of Cyclopropanols

Kulinkovich, O. G.

doi:10.1021/cr010012i

Cited by 471 publications

(203 citation statements)

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“…The temperature was elevated to ambient (20-21 °C) and the reaction mixture was stirred for 6 h. The reaction mixture was worked up with 7-10% aq. HCl, the reaction products were extracted with diethyl ether, dried with Na 2 CO 3 …”

Section: Methodsmentioning

confidence: 99%

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One-pot synthesis of small spirocarbocycles through the catalytic cyclometalation reactions of unsaturated compounds

D’yakonov¹,

Tuktarova²,

Trapeznikova³

et al. 2010

Arkivoc

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Dedicated to Professor Usein M. Dzhemilev on the occasion of his 65th birthday AbstractThe mild and efficient one-pot methods to synthesize substituted spirocyclopropanes and spirocyclobutanes are reported. The elaborated procedures based on consecutive cycloalumination of methylenecyclopropanes, methylenecyclobutanes or cycloalkynes assisted by alkyl aluminums and Cp 2 ZrCl 2 as a catalyst provide the formation of target products through Pd catalyzed carbocyclization of the aluminacyclopentane and aluminacyclopentene intermediates with Me 2 SO 4 or allyl chloride.

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Section: Methodsmentioning

confidence: 99%

“…Of real interest are the methods, elaborated in the last 10-15 years, for the construction of cyclopropane alcohols 3 and ethers 4 by the interaction between esters and Grignard reagents or alkylhalogenalanes in the presence of Ti and Zr complexes through the three-membered metallacarbocycles.…”

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confidence: 99%

One-pot synthesis of small spirocarbocycles through the catalytic cyclometalation reactions of unsaturated compounds

D’yakonov¹,

Tuktarova²,

Trapeznikova³

et al. 2010

Arkivoc

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“…Auf dieser Grundlage wurden b-Acetoxyquecksilberketone [38,39] aus Siloxycyclopropanen synthetisiert. Enantiomerenreine Cyclopropanole [40] 33 wurden unter Erhaltung der Enantiomerenverhältnisse in offenkettige Alkohole 34 umgesetzt (Schema 14). [41] Die stereospezifische Oxymercurierung von Cyclopropanolen, [41] in Kombination mit einer durch Sauerstoff dirigierten Cyclopropanierung acyclischer Alkohole, [42,43] schuf einen direkten und stereoselektiven Zugang zu verschieden substituierten Polypropionatfragmenten.…”

Section: Introductionunclassified

“…[54] Desweiteren sind auch Iridiumkatalysatoren wie [{Cp*IrCl 2 } 2 ] in der Lage, hocheffizient Cyclopropanole in a-Alkylketone zu überfüh-ren. [56] Es ist naheliegend, dass die direkte Umsetzung von Cyclopropanol 46, das leicht durch Kulinkovitch-Cyclopropanierung zugänglich ist, [40] [33,63] Diese Art von C-C-Bindungsspaltungen wurden kürzlich mit dem Konzept der C-H-Aktivierung vereint, was die Mçglichkeit erçffnet, w-En-Cyclopropane 55 mithilfe eines einzigen metallorganischen Reagens in die funktionalisierten Produkte 56 zu überführen. [31] Dieser "Zirconium-Lauf" wurde bereits für die Umsetzung von einfachen w-ungesättigten Fettalkoholen, [32] nichtkonjugierten w-Enolethern [35,64,65] und Alkylidencyclopropanen [31] zu Allyl-, Dienyl-und Cyclobutylzirconocenen etabliert.…”

Section: Introductionunclassified

Selektive C‐C‐Bindungsspaltung zur stereoselektiven Synthese acyclischer Systeme

et al. 2014

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Chemiker setzen seit jeher auf die Entwicklung kreativer Strategien zum Aufbau von Kohlenstoff‐Kohlenstoff‐ und Kohlenstoff‐Heteroatom‐Bindungen. Innerhalb dieses Aufsatzes wird ein weiterer Ansatz eingeführt, der schwierige Molekülstrukturen durch selektive C‐C‐Bindungsspaltung zugänglich macht. Obwohl C‐C‐Einfachbindungen nur eingeschränkt reaktiv sind, soll gezeigt werden, dass diese Methodik einen regio‐, diastereo‐ und enantioselektiven Zugang zu facettenreichen Produkten bietet. Die Entwicklung solcher Strategien mag in Zukunft einen schwerwiegenden Einfluss auf die Syntheseplanung haben und zu neuen und innovativen Prozessen unter Verwendung einfacher oder komplexer Kohlenwasserstoffe führen.

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“…Enantioenriched oxasilolanes are easily converted into cyclopropanols, a useful building block in organic synthesis. [38] For example, the treatment of oxasilolane 3a with TBAF, aqueous H 2 O 2 , and KHCO 3 formed cyclopropanol 7 without any erosion in ee (eq 2). [39] The absolute configurations of the stereogenic centers in 7 were unambiguously determined by single-crystal X-ray analysis.…”

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Rhodium‐Catalyzed Enantioselective Silylation of Cyclopropyl C−H Bonds

Lee

Hartwig

2016

Angewandte Chemie

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We describe an enantioseleclive silylation of cyclopropanes catalyzed by a rhodium precursor and the bisphosphine (S)-DTBM-SEGPHOS. (Hydrido)silyl ethers, generated in situ by the dehydrogenative silylation of cyclopropylmethanols with diethylsilane, undergo asymmetric, intramolecular silylation of cyclopropyl C-H bonds in high yields with high enantiomeric excesses in the presence of the rhodium catalyst. The resulting enantioenriched oxasilolanes are suitable substrates for Tamao-Fleming oxidation to form cyclopropanols with conservation of the ee from the C-H bond silylation. Preliminary mechanistic data suggest that C-H cleavage is likely to be the turnover-limiting and enantioselectivity-determining step. Graphical Abstract(Hydrido)silyl ethers, generated in situ by the dehydrogenative silylation of cyclopropylmethanols with diethylsilane, undergo asymmetric, intramolecular silylation of cyclopropyl C-H bonds in high yields with high enantiomeric excesses in the presence of a rhodium catalyst. The silylation products are suitable substrates for Tamao-Fleming oxidation to form cyclopropanols with conservation of the ee from the C-H bond silylation.Keywords asymmetric catalysis; C-H activation; cyclopropane; rhodium; silylation The functionalization of C-H bonds with boranes and silanes has been studied intensively, due to the high regioselectivity of these processes for sterically accessible C-H bonds and widespread utility of the products. [1,2] However, the development of enantioselective variants of these reactions, particularly enantioselective functionalization of alkyl C-H bonds, has been limited (Scheme 1). [3][4][5] Kuninobu, Murai and Takai reported the Correspondence to: John F. Hartwig, jhartwig@berkeley.edu. Supporting information for this article is given via a link at the end of the document. HHS Public Access Author ManuscriptAuthor Manuscript Author ManuscriptAuthor Manuscript asymmetric silylation of a C-H bond to generate a stereogenic silicon center with up-to 88% enantiomeric excess (ee) (Scheme 1A). [6,7] Shibata, He, Murai and Takai independently reported the synthesis of planar chiral compounds with moderate to high enantioselectivities by asymmetric C-H silylation of ferrocenes. [8][9][10] Recently, we reported an enantioselective silylation of aryl C-H bonds to form enantioenriched benzoxasilole products with up-to 99% ee. [11] Although these reactions can occur with high enantioselectivity, they are limited to the functionalization of aryl C-H bonds. The only published set of enantioselective silylations of alkyl C-H bonds occurs with low ee (37-40% ee) and with limited scope (Scheme 1B). [12] To create the first silylations of alkyl C-H bonds that occur with high enantioselectivity, we investigated systems for the reactions of cyclopropanes. C-H bonds of cyclopropanes are more reactive than sp 3 C-H bonds of unstrained rings or alkyl chains, [13] and the rigid conformation of a cyclopropane could allow for high stereoselectivity. Yu and co-workers reported enantioselective...

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The Chemistry of Cyclopropanols

Abstract: Scheme 14Scheme 9 a a R′′ ) i-Pr or R′.

Cited by 471 publications

References 377 publications

One-pot synthesis of small spirocarbocycles through the catalytic cyclometalation reactions of unsaturated compounds

One-pot synthesis of small spirocarbocycles through the catalytic cyclometalation reactions of unsaturated compounds

Selektive C‐C‐Bindungsspaltung zur stereoselektiven Synthese acyclischer Systeme

Rhodium‐Catalyzed Enantioselective Silylation of Cyclopropyl C−H Bonds

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