The sisyl (tris(trimethylsilyl)silyl) group: A fluoride resistant, photolabile alcohol protecting group

Brook, Michael A.; Gottardo, Christine; Balduzzi, Sonya; Mohamed, Mustafa

doi:10.1016/s0040-4039(97)01673-0

Cited by 47 publications

(25 citation statements)

References 28 publications

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“…A bulky sisyl (tris(trimethylsilyl)) group has been introduced as a photocleavable protecting group for primary and secondary alcohols. 381 It was shown that it is stable to aqueous bases and Grignard and Wittig reagents, as well as resistant to selected fluoride salts. Irradiation of sisyl ethers at 254 nm leads to the deprotection of the alcohols in good chemical yields (62–95%) 382 by a radical mechanism.…”

Section: Miscellaneous Groupsmentioning

confidence: 99%

Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

et al. 2012

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Section: Miscellaneous Groupsmentioning

confidence: 99%

Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

et al. 2012

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“…Fortunately, addition of lithium tetrafluoroborate allowed for the generation of (±)-61 and other isomers in 64% yield. Diastereoselective ketone reduction with NaBH 4 followed by photolytic cleavage of the super silyl groups [91,92] and methylation gave the natural product (±)-58 in a total of ten steps, seven in the longest linear sequence.…”

Section: Total Synthesis Of Natural Products Using Supersilyl Aldol Rmentioning

confidence: 99%

Supersilyl Protective Groups in Aldol Reactions

Brady

Yamamoto

2013

Modern Methods in Stereoselective Aldol Reactions

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“…Indeed, such a group was introduced in 1997, namely the tris(trimethylsilyl(silyl)), also called the sisyl group (Scheme 13.18) [67,68]. This group is reported as being fluoride-resistant under carefully controlled conditions (CsF or KF/18-crown-6), but to be photosensitive at short wavelengths (between 200 and 300 nm apparent attraction, it has rarely been used in organic synthesis, most likely due to its overall sensitivity towards common conditions in organic synthesis (e.g., BuLi, LiAlH 4 , TBAF.).…”

Section: Silicon Ethersmentioning

confidence: 99%

Photolabile Protecting Groups in Organic Synthesis

Bochet

Blanc

2009

Handbook of Synthetic Photochemistry

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Protecting groups are crucial tools in organic synthesis, and their involvement increases with the length of a synthetic route. However, as their number increases within the same molecule, the problem of their individual and selective removal becomes a critical issue. This is well known as the orthogonality problem. Two groups are called orthogonal if they can be removed selectively under specific reaction conditions without mutual interference, and in any given sequence [1]. Unfortunately, the dimensions in the space of orthogonal groups are limited. Such dimensions are traditionally acidic, basic, nucleophilic, reductive, and oxidative conditions. A few more exotic specific conditions exist (and are highly desirable), and photolability is clearly one of these. It is attractive because no other reagent than light is required, thus limiting the chances of interference. Of course, the intrinsic photoreactivity of the remaining functional groups of the molecule is a liability, and many of the chapters in this Handbook have covered this topic. Thus, in order to have only reactivity at the desired sitethat is, removal of the protecting groupit is necessary to have a high absorbance of that group and a high quantum yield for its cleavage, to ensure that only short irradiation times are required.As the field of photolabile protecting groups (PPGs) has been reviewed on several occasions [2][3][4][5][6][7][8], the aim of this chapter is not to update the existing catalogues of groups. Indeed, when photolability has been selected as a candidate to solve a problem, the plethora of groupssometimes with contradictory behaviors and reaction conditionsmight deter even the most daring synthetic chemist. In an attempt to better guide the experimentalist, the decision was taken to divide the groups into major families based on a specific reaction, and then to list the variations on the groups, detailing their effects on reactivity. The application of photolabile protecting groups to the chemical functions is reported in Appendix 13.6, followed by a list of typical conditions and yields for protection and deprotection procedures.Handbook of Synthetic Photochemistry. Edited

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The sisyl (tris(trimethylsilyl)silyl) group: A fluoride resistant, photolabile alcohol protecting group

Cited by 47 publications

References 28 publications

Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

Supersilyl Protective Groups in Aldol Reactions

Photolabile Protecting Groups in Organic Synthesis

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