3-TMS-cyclopentene-1 a new reagent for the synthesis of cyclopentene derivatives

Ojima, Iwao; Kumagai, Miyoko; Miyazawa, Yuji

doi:10.1016/s0040-4039(01)93050-3

Cited by 40 publications

(8 citation statements)

References 8 publications

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“…102,103 Alkynyl ketones (88) behave like substituted alkynes (29). Thus, the triple bond reacts first to give vinylsilanes (89) and/or (90) (equation 56), which are sometimes reduced further to allyl silyl ethers (91) and/or (92). 104 As an alternative route to the reduction of <x,(3-unsaturated ketones accompanied by introduction of a silyl group at the (3-position, a silylcuprate reagent is applicable (equation 57).24b…”

Section: R3si~~s Ir3mentioning

confidence: 99%

Hydrosilylation of CC and CC

Hiyama

Kusumoto

1991

Comprehensive Organic Synthesis

127

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Section: R3si~~s Ir3mentioning

confidence: 99%

Hydrosilylation of CC and CC

Hiyama

Kusumoto

1991

Comprehensive Organic Synthesis

127

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“…Although 2: 1 telomerization reactions can be considered as a special case of 1,Caddition to a conjugated diene by a carbon nucleophile and a second nucleophile [Eq. (14)], these reactions will not be covered by this chapter. The reader is advised to consult Refs.…”

Section: 4-coupling With Rand Numentioning

confidence: 99%

“…0Ac)z + H202 Scheme 8-13 Mechanism of aerobic cis-1 ,Cdiacetoxylation.Intramolecular 1,4-diacyloxylationAn intramolecular variant of palladium-catalyzed 1 ,Cdiacetoxylation was developed by utilizing dienes with a carboxyl group in the side chain (Scheme[8][9][10][11][12][13][14] 166,671. In this case also, the stereochemistry of the I,4-addition can be controlled by variations of the ligand environment.…”

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confidence: 99%

Palladium‐Catalyzed 1,4‐Additions to Conjugated Dienes

Bäckvall¹

1998

Metal‐Catalyzed Cross‐Coupling Reactions

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Additions to nonactivated olefins and dienes are important reactions in organic synthesis [ 11. Although cycloadditions may be used for additions to double bonds, the most common way to achieve such reactions is to activate the olefins with an electrophilic reagent. Electrophilic activation of the olefin or diene followed by a nucleophilic attack at one of the sp2 carbon atoms leads to a 1,2-or lA-addition. More recently, transition metals have been employed for the electrophilic activation of the double bond [2]. In particular, palladium(I1) salts are known to activate carbon-carbon double bonds toward nucleophilic attack [3] and this is the basis for the Wacker process for industrial oxidation of ethylene to acetaldehyde [4]. In this process, the key step is the nucleophilic attack by water on a (n-ethy1ene)palladium complex.Additions to conjugated dienes constitute a special class of reactions, in which it is of great importance to control the regioselectivity toward 1,2-or 1,4-addition. With classical electrophilic reagents, it is difficult to control the regioselectivity: often, mixtures of 1,2and 1,4-regioisomers are formed. With the use of transition metals, highly regioselective additions to conjugated dienes can sometimes be obtained [5]. From a synthetic point of view, this regioselectivity is of great importance if these additions are catalyzed by the metal. One metal that has been successfully used in this respect is palladium. Several reviews have included palladium-catalyzed additions to conjugated dienes [5-101. The present review deals with palladium-catalyzed reactions leading to selective bis-couplings in the 1and 4-positions of 1,3-dienes.Palladium-catalyzed 1,4-additions to conjugated dienes can be divided into two classes: (1) non-oxidation reactions that (2) oxidation reactions. In the former class, a palladium(0) catalyst is employed and the first step in the catalytic cycle is often an activation of one of the reactants by its oxidative addition to Pd(0). In the second class, a palladium(I1) complex is the active catalyst which oxidizes the substrate diene with formation of Pd(0). Reoxidation of Pd(0) to Pd(II) by an oxidant regenerates the active catalyst. Palladium(0)-catalyzed ReactionsThese are non-oxidation reactions that can be divided into several subclasses. The active catalyst is a palladium(0) complex, such as Pd(PPh,), or some analogous phosphine complex. Such palladium(0)-phosphine complexes may also be generated in situ fromMetal-catalyzed Cross-coupling Reactions Edited by François Diederich, Peter J. Stang 340 8 Palladium-catulyzed 1,4-Additions the latter case Pd(I1) is reduced to Pd(0) by the phosphine [ 111. A common feature of the palladium(0)-catalyzed additions to conjugated dienes is that they begin with an oxidative addition of a species such as H-Nu or RX to palladium(0) to give a pdlladium(l1)-hydride complex or an organometallic R-Pd(I1) complex, respectively. These complexes subsequently react with the conjugated diene in a migratory insertion reaction to give...

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“…291 The synthetic potential of disilylalkenes 5 is indicated in Scheme 4 . Acylation of 5a or 5d with benzoyl chloride/aluminium trichloride [4] [15] at -70" in CH,C12 yields the corresponding (E)-vinylsilanes 6a and 6d (76% and 61% respectively). Vinylsilane 6a was desilylated by hydrogen iodide in benzene [I61 yielding 7 (75%).…”

Section: -mentioning

confidence: 99%

“…For a general method using 2-(trimethylsilyl)ethylidene(triphenyl)phosphorane [3]; hydrosilylation of cyclopentadiene [4]; allylmagnesium compounds and chlorosilanes [5]; by cycloadditions [6]. [7].…”

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confidence: 99%

1,1‐Disilyl‐2‐Alkenes: Preparation and Some Synthetic Applications. Preliminary communication

Wetter¹

1978

Helvetica Chimica Acta

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SummaryAlly1 sulfides and a selenide are metallated and silylated with chloro (pentamethy1)disilane. Treatment of the resulting disilanylmethyl sulfides 4 with trimethyloxonium tetrafluoroborate furnishes l,l-disilyl-2-alkenes 5 in good yields. Some synthetic possibilities of 5 are outlined.The synthetic utility of allylsilanes 1 and vinylsilanes 2 has been amply demonstrated [ 11 (Scheme 1). Whereas there are convenient methods to prepare vinylsilanes2), routes to allylsilanes3) are mostly complicated and often leading to mixtures. We describe an easy way to convert allyl sulfides 3 and an allyl selenide via the corresponding disilanes 4 to substituted l,l-disilyl-2-alkenes 5. Based on the observation by Kumada of a facile disilane-disilylmethane rearrangement4) the Schema I

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3-TMS-cyclopentene-1 a new reagent for the synthesis of cyclopentene derivatives

Cited by 40 publications

References 8 publications

Hydrosilylation of CC and CC

Hydrosilylation of CC and CC

Palladium‐Catalyzed 1,4‐Additions to Conjugated Dienes

1,1‐Disilyl‐2‐Alkenes: Preparation and Some Synthetic Applications. Preliminary communication

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