Reactions of a highly crowded cyclic stannylene with iodoalkanes, enones, and dienes. Inhibition of nucleophilic substitution at tin(IV) centers

Ashrafolmolouk Asadi; Colin Eaborn; Michael S. Hill; Peter B. Hitchcock; Michael M. Meehan; J. David Smith

doi:10.1021/om020106y

Reactions of a highly crowded cyclic stannylene with iodoalkanes, enones, and dienes. Inhibition of nucleophilic substitution at tin(IV) centers

Ashrafolmolouk Asadi, Colin Eaborn, Michael S. Hill, Peter B. Hitchcock, Michael M. Meehan, J. David Smith

University of Sussex

Research output: Contribution to journal › Article › peer-review

29 Citations (SciVal)

Abstract

The cyclic stannylene RSnR (2; RR = C(SiMe₃)₂SiMe₂CH₂CH₂Me ₂Si(Me₃Si)₂C) reacted with alkyl iodides R′I (R′ = Et, ⁱPr) to give the Sn^IV compounds RSnR′IR (6b,c), which were converted by treatment with silver trifluoroacetate into RSnR′(OCOCF₃)R (7b,c). Reaction of the stannylene 2 with appropriate enones or diones yielded the products RRSnOC(Et)=CHCH₂ (10), RRSnOCPh=CPhO (11), RRSnOC₆H₂-3,5-^tBu₂O (12), and RRSnOC₁₄H₃O (13) (OC₁₄H₈O = 9,10-phenanthrenediolato). The crystal structures of 6b, 7b,c, and 10-13 have been determined. Treatment of 2 with water, alcohols, or phenol led to ring opening. There is evidence from ESR spectroscopy that the oxidative additions of diones involve radical intermediates. The compound RSnMeIR (6a) reacted with ICI to give the chloride RSnMeClR (15), but, in contrast to the previously described crowded trialkyltin halides (Me₃Si)₃CSnMe₂X (X = Cl, I), neither 6a nor 15 reacted with nucleophilic reagents.

Original language	English
Pages (from-to)	2430-2437
Number of pages	8
Journal	Organometallics
Volume	21
Issue number	12
DOIs	https://doi.org/10.1021/om020106y
Publication status	Published - 10 Jun 2002

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{c6394b8f5db349c4a9e3d0b19406e46c,

title = "Reactions of a highly crowded cyclic stannylene with iodoalkanes, enones, and dienes. Inhibition of nucleophilic substitution at tin(IV) centers",

abstract = "The cyclic stannylene RSnR (2; RR = C(SiMe3)2SiMe2CH2CH2Me 2Si(Me3Si)2C) reacted with alkyl iodides R′I (R′ = Et, iPr) to give the SnIV compounds RSnR′IR (6b,c), which were converted by treatment with silver trifluoroacetate into RSnR′(OCOCF3)R (7b,c). Reaction of the stannylene 2 with appropriate enones or diones yielded the products RRSnOC(Et)=CHCH2 (10), RRSnOCPh=CPhO (11), RRSnOC6H2-3,5-tBu2O (12), and RRSnOC14H3O (13) (OC14H8O = 9,10-phenanthrenediolato). The crystal structures of 6b, 7b,c, and 10-13 have been determined. Treatment of 2 with water, alcohols, or phenol led to ring opening. There is evidence from ESR spectroscopy that the oxidative additions of diones involve radical intermediates. The compound RSnMeIR (6a) reacted with ICI to give the chloride RSnMeClR (15), but, in contrast to the previously described crowded trialkyltin halides (Me3Si)3CSnMe2X (X = Cl, I), neither 6a nor 15 reacted with nucleophilic reagents.",

author = "Ashrafolmolouk Asadi and Colin Eaborn and Hill, {Michael S.} and Hitchcock, {Peter B.} and Meehan, {Michael M.} and Smith, {J. David}",

year = "2002",

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language = "English",

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T1 - Reactions of a highly crowded cyclic stannylene with iodoalkanes, enones, and dienes. Inhibition of nucleophilic substitution at tin(IV) centers

AU - Asadi, Ashrafolmolouk

AU - Eaborn, Colin

AU - Hill, Michael S.

AU - Hitchcock, Peter B.

AU - Meehan, Michael M.

AU - Smith, J. David

PY - 2002/6/10

Y1 - 2002/6/10

N2 - The cyclic stannylene RSnR (2; RR = C(SiMe3)2SiMe2CH2CH2Me 2Si(Me3Si)2C) reacted with alkyl iodides R′I (R′ = Et, iPr) to give the SnIV compounds RSnR′IR (6b,c), which were converted by treatment with silver trifluoroacetate into RSnR′(OCOCF3)R (7b,c). Reaction of the stannylene 2 with appropriate enones or diones yielded the products RRSnOC(Et)=CHCH2 (10), RRSnOCPh=CPhO (11), RRSnOC6H2-3,5-tBu2O (12), and RRSnOC14H3O (13) (OC14H8O = 9,10-phenanthrenediolato). The crystal structures of 6b, 7b,c, and 10-13 have been determined. Treatment of 2 with water, alcohols, or phenol led to ring opening. There is evidence from ESR spectroscopy that the oxidative additions of diones involve radical intermediates. The compound RSnMeIR (6a) reacted with ICI to give the chloride RSnMeClR (15), but, in contrast to the previously described crowded trialkyltin halides (Me3Si)3CSnMe2X (X = Cl, I), neither 6a nor 15 reacted with nucleophilic reagents.

AB - The cyclic stannylene RSnR (2; RR = C(SiMe3)2SiMe2CH2CH2Me 2Si(Me3Si)2C) reacted with alkyl iodides R′I (R′ = Et, iPr) to give the SnIV compounds RSnR′IR (6b,c), which were converted by treatment with silver trifluoroacetate into RSnR′(OCOCF3)R (7b,c). Reaction of the stannylene 2 with appropriate enones or diones yielded the products RRSnOC(Et)=CHCH2 (10), RRSnOCPh=CPhO (11), RRSnOC6H2-3,5-tBu2O (12), and RRSnOC14H3O (13) (OC14H8O = 9,10-phenanthrenediolato). The crystal structures of 6b, 7b,c, and 10-13 have been determined. Treatment of 2 with water, alcohols, or phenol led to ring opening. There is evidence from ESR spectroscopy that the oxidative additions of diones involve radical intermediates. The compound RSnMeIR (6a) reacted with ICI to give the chloride RSnMeClR (15), but, in contrast to the previously described crowded trialkyltin halides (Me3Si)3CSnMe2X (X = Cl, I), neither 6a nor 15 reacted with nucleophilic reagents.

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Reactions of a highly crowded cyclic stannylene with iodoalkanes, enones, and dienes. Inhibition of nucleophilic substitution at tin(IV) centers

Abstract

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