Aluminum Chloride Catalyzed Regioselective Allylsilylation of Alkenes: Convenient Route to 5-Silyl-1-alkenes

Yeon, Seung Ho; Lee, Bong Woo; Yoo, Bok Ryul; Suk, Mi-Yeon; Jung, Il Nam

doi:10.1021/om00005a037

Cited by 33 publications

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“…A silyl cation or a complex intermediate I is directly formed at the beginning stage of the reaction from aluminum chloride and trimethylchlorosilane, [14][15][16] or from the protodesilylation of allyltrimethylsilane by acids resulting from the reaction of anhydrous aluminum chloride with adventitious water in the reaction mixture. 13,[19][20][21] coming allylsilane, followed by elimination of the trimethylsilyl cation as illustrated in Scheme 1.…”

Section: Equationmentioning

confidence: 99%

“…Regiospecific addition and allylic inversion were also found to be characteristic of the allylsilylation of alkenes. 13,14 Reaction of 3c with 1b having a methyl group b to the silicon did not proceed in hexane solution but in methylene chloride, a solvent known to be effective in Lewis acid catalyzed reactions. 25,26 The unusual product 4c' (36%) was obtained as a major product along with the expected normal allylsilylated product, 4,6-bis(trimethylsilylmethyl)-2-methyl-1-undecene (4c, 3%).…”

Section: Equationmentioning

confidence: 99%

“…The results are consistent with the formation of silyl cations in these allylsilylations. [13][14][15][16] Equation 8 To confirm that the isomerization had occurred under the allylsilylation reaction conditions, compound 3i was tested using the same reaction conditions but in the absence of 1a. 12% of 3i was converted to give the isomeric product, 3-[3-(trimethylsilyl)propyl]cyclopentene (3i') in 11% yield in 30 min (eq 9).…”

Section: Equationmentioning

confidence: 99%

“…Intermediate I, generated as described in Scheme 1, interacts with 3 to form a new intermediate II which is stabilized by the silyl b-stabilization effect. 13 …”

Section: Equationmentioning

confidence: 99%

“…This result suggests that s-p interactions in the allylsilylation of diallylsilane are less important than in the allylsilylation of monoallylsilane. [13][14][15][16] …”

Section: Equation 10mentioning

confidence: 99%

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Lewis Acid-Catalyzed Regio- and Stereoselective Allylsilation of Simple Unsaturated Hydrocarbons

Jung¹,

Yoo²

1999

Synlett

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The reactions of allylsilanes with unsaturated hydrocarbons such as alkenes and alkynes in the presence of Lewis acid catalyst give regio-and stereospecific trans-allylsilylated products in good yields. In the allylsilylations of terminal alkenes and alkynes, the silyl group adds to the terminal carbon and the allyl group adds to the inner carbon of the multiple bonds. Reaction with cyclic olefins gives allylsilylated products having the silyl and allyl groups in trans positions. In allylsilylations with the stereohomogeneous (Z)crotyltrimethylsilane, an allylic inversion is observed indicating a stepwise allylsilylation process. The reaction of conjugated dienes with allylsilanes gives [3+2] annulation products having the silyl and the vinyl groups in trans positions on the ring. Allylsilylation of 5-(trimethylsilyl)-1-pentenes gives unusual allylsilylated products through an intramolecular 1,5-hydride rearrangement reaction in the normal allylsilylated products. All results are consistent with the involvement of silylenium ions in the allylsilylations. 1 Introduction 2 Allylsilylation of Alkenes 2.1 Linear Alkenes 2.2 Cyclic Alkenes 2.3 5-(Trimethylsilyl)-1-pentene 3 Allylsilylation and Intramolecular Cyclization of Diallylsilanes 4 Allylsilylation and [3+2] Cycloaddition of Conjugated Dienes 4.1 Linear Conjugated Dienes 4.2 Cyclic Conjugated Dienes 5 Allylsilylation of Alkynes 5.1 Terminal Alkynes 5.2

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Section: Equationmentioning

confidence: 99%

Section: Equationmentioning

confidence: 99%

Section: Equationmentioning

confidence: 99%

“…Intermediate I, generated as described in Scheme 1, interacts with 3 to form a new intermediate II which is stabilized by the silyl b-stabilization effect. 13 …”

Section: Equationmentioning

confidence: 99%

“…This result suggests that s-p interactions in the allylsilylation of diallylsilane are less important than in the allylsilylation of monoallylsilane. [13][14][15][16] …”

Section: Equation 10mentioning

confidence: 99%

See 3 more Smart Citations

Lewis Acid-Catalyzed Regio- and Stereoselective Allylsilation of Simple Unsaturated Hydrocarbons

Jung¹,

Yoo²

1999

Synlett

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Allyltrimethylsilane

Fleming

Asao

2006

Encyclopedia of Reagents for Organic Synthesis

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Activating and Directive Effects of Silicon

Bassindale¹,

Glynn²,

Taylor³

2009

Patai's Chemistry of Functional Groups

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Introduction Electronic Effects of R 3 Si The Measurement and Interpretation of R 3 Si Activating and Directive Parameters Activating and Directive Effects of Silicon in Electrophilic Aromatic Substitution Activating and Directive Effects in Aliphatic Electrophilic Reactions Activating and Directive Effects of Silicon in Carbanionic Reactions Stabilization of Developing Negative Charge by Silicon

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Aluminum Chloride Catalyzed Regioselective Allylsilylation of Alkenes: Convenient Route to 5-Silyl-1-alkenes

Cited by 33 publications

References 0 publications

Lewis Acid-Catalyzed Regio- and Stereoselective Allylsilation of Simple Unsaturated Hydrocarbons

Lewis Acid-Catalyzed Regio- and Stereoselective Allylsilation of Simple Unsaturated Hydrocarbons

Allyltrimethylsilane

Activating and Directive Effects of Silicon

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