Vinylsilanes

Colvin, Ernest W.

doi:10.1016/b978-0-408-10831-7.50013-5

Cited by 22 publications

(9 citation statements)

References 107 publications

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“…NMR (CDCI3, 300 MHz) ó 0.88 (t, J = 7.4 Hz, 3 ), 1.24 (t, J = 7.1 Hz, 3 ), 1.53-1.65 (m, 2 H), 2.38-2.59 (m, 4 ), 3.50 (t, J = 7.4 Hz, 1 ), 4.16 (q, J = 7.1 Hz, 2 ), 4.49-5.09 (m, 2 H), 5.64-5.78 (m, 1 H); 13C NMR (CDCI3, 75 MHz) ó 13. 47, 14.03, 16.77, 32.13, 43.97, 58.45, 61.27,117.28,134.33,169.22, 204.52; IR (neat) Ethyl 2-Acetyl-2-methyl-4-pentenoate (19). The standard procedure 1 was followed by use of ethyl 2-methylacetoacetate (18, 69.3 mg, 0.481 mmol, 1.0 equiv), allyltrimethylsilane (73.8 mg, 0.646 mmol, 1.3 equiv), CAN (571 mg, 1.04 mmol, 2.1 equiv), and methanol (10 mL).…”

Section: Discussionmentioning

confidence: 99%

Silicon-Controlled Allylation of 1,3-Dioxo Compounds by Use of Allyltrimethylsilane and Ceric Ammonium Nitrate

Hwu¹,

Chen²,

Shiao³

1995

J. Org. Chem.

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A new method was developed for allylation of 1,3-diketones, ß-keto esters, and malonates. Treatment of those 1,3-dioxo compounds with allyltrimethylsilane (1.3 equiv) in the presence of ceric ammonium nitrate (2.1 equiv) in methanol at room temperature often gave the mono-Callylated products in good to excellent yields (74-98%). These reactions, involving /3-carboradical and /3-carbocationic intermediates, were controlled by a silyl group. Replacement of ceric ammonium nitrate and methanol with manganese(III) acetate (2.4 equiv) and acetic acid afforded siliconcontaining dihydrofurans in high yields at 80 °C.

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Section: Discussionmentioning

confidence: 99%

Silicon-Controlled Allylation of 1,3-Dioxo Compounds by Use of Allyltrimethylsilane and Ceric Ammonium Nitrate

Hwu¹,

Chen²,

Shiao³

1995

J. Org. Chem.

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“…Whereas dehydrogenative silylation of alcohols with hydrosilanes is well studied, dehydrogenative silylation of alkenes with hydrosilanes is relatively unexplored. From a synthetic point of view, the reaction is important because the product is a vinylsilane a reaction in which there are regio- and stereochemical problems.…”

Section: Introductionmentioning

confidence: 99%

Cationic Rhodium Complex-Catalyzed Highly Selective Dehydrogenative Silylation of Styrene

and

Yasue

1996

Organometallics

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Cationic rhodium complex-catalyzed dehydrogenative silylation of styrene with hydrosilanes was studied. Dehydrogenative silylation was competitive with hydrosilylation. The selectivity was strongly dependent on the reaction temperature and the molar ratio of styrene to hydrosilane. The selectivity of dehydrogenative silylation was 92% when using 3 equiv of styrene to 1 equiv of triethylsilane (1a) in refluxing diethyl ketone. The nature of the hydrosilane also affected the reaction. As the steric bulk of hydrosilane increased, the selectivity of dehydrogenative silylation increased. Dehydrogenative silylation product (2d) was obtained exclusively in 81% yield when using triisopropylsilane (1d). The amount of ligand had a large influence on the selectivity of the reaction. As the amount of PPh3 used increased, the selectivity of dehydrogenative silylation increased. These results were reasonably explained according to the mechanism involving the insertion of styrene into the rhodium−silicon bond which was formed by the oxidative addition of hydrosilane to rhodium complex.

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“…Allyl- and enolsilanes serve as important substrates in numerous synthetically useful ground and excited state reactions [ 53 – 54 ]. The most common roles of these substances are to act as the respective equivalents of allylic anions and enolate ions.…”

Section: Reviewmentioning

confidence: 99%

Direct and indirect single electron transfer (SET)-photochemical approaches for the preparation of novel phthalimide and naphthalimide-based lariat-type crown ethers

Cho

Mariano²,

Yoon³

2014

Beilstein J. Org. Chem.

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SummaryIn this review, we describe direct and indirect photochemical approaches that have been developed for the preparation of phthalimide- and naphthalimide-based, lariat-type crown ethers. The direct route utilizes a strategy in which nitrogen-linked side chains containing polyethoxy-tethered phthalimides and naphthalimides, possessing terminal α-trialkylsilyl groups, are synthesized utilizing concise routes and UV-irradiation to form macrocyclic ring systems. In contrast, the indirect route developed for the synthesis of lariat-type crown ethers employs sequences in which SET-promoted macrocyclization reactions of α-trialkylsilyl-terminated, polyethoxy-tethered phthalimides and naphthalimides are followed by a side chain introduction through substitution reactions at the amidol centers in the macrocyclic ethers. The combined observations made in these investigations demonstrate the unique features of SET-promoted photocyclization reactions that make them well-suited for the use in the synthesis of functionalized crown ethers. In addition, while some limitations exist for the general use of SET-photochemical reactions in large-scale organic synthesis, important characteristics of the photoinduced macrocyclization reactions make them applicable to unique situations in which high temporal and spatial control is required.

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Vinylsilanes

Cited by 22 publications

References 107 publications

Silicon-Controlled Allylation of 1,3-Dioxo Compounds by Use of Allyltrimethylsilane and Ceric Ammonium Nitrate

Silicon-Controlled Allylation of 1,3-Dioxo Compounds by Use of Allyltrimethylsilane and Ceric Ammonium Nitrate

Cationic Rhodium Complex-Catalyzed Highly Selective Dehydrogenative Silylation of Styrene

Direct and indirect single electron transfer (SET)-photochemical approaches for the preparation of novel phthalimide and naphthalimide-based lariat-type crown ethers

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