Mechanistic photochemistry of acylsilanes. 1. Reaction with alcohols

Bourque, Robert A.; Davis, Paul D.; Dalton, J. Christopher

doi:10.1021/ja00393a048

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“…In this case, the acetal is formed by the photochemical generation of a silyloxycarbene from the acyl silane, which then inserts into the O H bond of a solvent molecule (Scheme 90). Dalton has examined the kinetics of the latter reaction and have confirmed that acetal formation occurs exclusively through reaction of alcohol with an intermediate presumed to be the silyloxycarbene, generated from the acyl silane T1 state 204 Silyloxycarbenes are also formed on heating acyl silanes; intramolecular C H bond insertion may then occur, as illustrated in Scheme 91 205 . Such an intramolecular insertion reaction of a silyloxycarbene generated from ortho-tolyl acyl trimethylsilane has been investigated as a potential route to benzocyclobutenols (Scheme 92) 206 .…”

Section: Photochemistrymentioning

confidence: 99%

Acyl Silanes

Page¹,

McKenzie²,

Klair³

et al. 2009

Patai's Chemistry of Functional Groups

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Section: Photochemistrymentioning

confidence: 99%

Acyl Silanes

Page¹,

McKenzie²,

Klair³

et al. 2009

Patai's Chemistry of Functional Groups

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“…A mechanistic study by Dalron ef al. disclosed that the formation of acctals upon irradiation of acylsilanes in the presence of alcohols occurred exclusively (;in the siloxycarbene intermediate formed from the acylsilane triplet state[6].…”

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Photochemical reactions. 139^th Communication. Photochemistry of acylsilanes: 1. Siloxcarbene formation versus γ‐H‐abstraction

Scheller

Frei

1984

Helvetica Chimica Acta

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Preparation of the Compounds 1 and -The acylsilane 1 and the methyl ketone 2 were synthesized starting from 7,8-dihydro-y-ionone 3 in 17 and 30% overall yields, respectively (see Scheme I ) . Reaction of the iodide 4 (obtained from 3 via 5+6+7 with the 2-lithio derivatives of 8') and 9 [9] [lo] gave the 1,3-dithianes 10 (92%) and 11 (94%) which were dethioacetalized by treatment with Tl(NO,),. 3H,O [ll] [12] affording 1 (54%) and 2 (88%), respectively.given in the Table and the photoproducts depicted in Scheme 2. 3. Photolysis Experiments. -3.1. Irradiation of the Acylsilane 1. The results are Scheme 2 OOH 12 19 13 1 17Prepared by reaction of 2-lithio-1,3-dithiane with (t-buty1)dimethylsilyl chloride

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“…Upon irradiation, acyl silanes undergo a 1,2-photo Brook rearrangement to reveal a stabilized α-siloxy carbene, which has since been shown to insert into a variety of acidic, polar, and non-polarized bonds to yield X–H insertion products in high yields (Figure 1B, 5 ). 14–20 The rearrangement occurs with high quantum yields to the α-siloxy carbene 21 at long UV wavelengths (350–420 nm) ideal for photocrosslinking. We became interested in utilizing the 1,2-photo Brook rearrangement as an orthogonal mechanism for carbene generation that could bypass deleterious competing pathways common to other carbene precursors, such as diazo formation from diazirines, 22 and provide complementary reactivity to known warheads (Fig.…”

Section: Introductionmentioning

confidence: 99%