Platinum-catalysed 1,4-diboration of 1,3-dienes

William Clegg, Thorsten R.F. Johann, Todd B. Marder, Nicholas C. Norman, A. Guy Orpen, Torren M. Peakman, Michael J. Quayle, Craig R. Rice, Andrew J. Scott

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Abstract

The chiral diborane(4) compounds B2[R,R-O2CH(CO2Me)CH(CO2Me)] 2, B2(S,O2CH2CHPh)2, B2(R,R-O2-CHPhCHPh)2 and B2(O2C20H12)2 (O2C20H12 = 1,7′-bi-2-naphtholate) have been synthesized. All four compounds have been characterised by X-ray crystallography, the latter as a racemate. The B-B bond oxidativeaddition reactions of the first three compounds with [Pt(PPh3)2(μ-C2H4)] resulted in the platinum(II) bis(boryl) complexes cis-[Pt(PPh3)2{B[R,R-O2CH(CO 2Me)CH(CO2Me)]}2], cis-[Pt(PPh3)2{B(S-O2CH2CHPh)} 2] and cis-[Pt(PPh3)2{B(R,R-O2CHPhCHPh)}2]; the former two were also characterised by X-ray crystallography. The platinum-catalysed diborations of a range of prochiral 1,3-dienes with the compounds B2[R,R-O2CH(CO2Me)-CH(CO2Me)] 2, B2(S-O2CH2CHPh)2 and B2(R,R-O2CHPhCHPh)2 were studied. Although these reactions were clean and quantitative, observed product d.e.s (measured by 1H NMR spectroscopy) were low or non-existent indicating that chirality transfer from the diborane(4) diolate groups to the diene diboration product is not efficient in these cases.

Original languageEnglish
Pages (from-to)1431-1438
Number of pages8
JournalJournal of the Chemical Society - Dalton Transactions
Issue number9
DOIs
Publication statusPublished - 7 May 1998
Externally publishedYes

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Carbon Monoxide
Platinum
X ray crystallography
Chirality
Nuclear magnetic resonance spectroscopy
diborane

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Clegg, W., Johann, T. R. F., Marder, T. B., Norman, N. C., Orpen, A. G., Peakman, T. M., ... Scott, A. J. (1998). Platinum-catalysed 1,4-diboration of 1,3-dienes. Journal of the Chemical Society - Dalton Transactions, (9), 1431-1438. https://doi.org/10.1039/a800108a
Clegg, William ; Johann, Thorsten R.F. ; Marder, Todd B. ; Norman, Nicholas C. ; Orpen, A. Guy ; Peakman, Torren M. ; Quayle, Michael J. ; Rice, Craig R. ; Scott, Andrew J. / Platinum-catalysed 1,4-diboration of 1,3-dienes. In: Journal of the Chemical Society - Dalton Transactions. 1998 ; No. 9. pp. 1431-1438.
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title = "Platinum-catalysed 1,4-diboration of 1,3-dienes",
abstract = "The chiral diborane(4) compounds B2[R,R-O2CH(CO2Me)CH(CO2Me)] 2, B2(S,O2CH2CHPh)2, B2(R,R-O2-CHPhCHPh)2 and B2(O2C20H12)2 (O2C20H12 = 1,7′-bi-2-naphtholate) have been synthesized. All four compounds have been characterised by X-ray crystallography, the latter as a racemate. The B-B bond oxidativeaddition reactions of the first three compounds with [Pt(PPh3)2(μ-C2H4)] resulted in the platinum(II) bis(boryl) complexes cis-[Pt(PPh3)2{B[R,R-O2CH(CO 2Me)CH(CO2Me)]}2], cis-[Pt(PPh3)2{B(S-O2CH2CHPh)} 2] and cis-[Pt(PPh3)2{B(R,R-O2CHPhCHPh)}2]; the former two were also characterised by X-ray crystallography. The platinum-catalysed diborations of a range of prochiral 1,3-dienes with the compounds B2[R,R-O2CH(CO2Me)-CH(CO2Me)] 2, B2(S-O2CH2CHPh)2 and B2(R,R-O2CHPhCHPh)2 were studied. Although these reactions were clean and quantitative, observed product d.e.s (measured by 1H NMR spectroscopy) were low or non-existent indicating that chirality transfer from the diborane(4) diolate groups to the diene diboration product is not efficient in these cases.",
author = "William Clegg and Johann, {Thorsten R.F.} and Marder, {Todd B.} and Norman, {Nicholas C.} and Orpen, {A. Guy} and Peakman, {Torren M.} and Quayle, {Michael J.} and Rice, {Craig R.} and Scott, {Andrew J.}",
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Clegg, W, Johann, TRF, Marder, TB, Norman, NC, Orpen, AG, Peakman, TM, Quayle, MJ, Rice, CR & Scott, AJ 1998, 'Platinum-catalysed 1,4-diboration of 1,3-dienes', Journal of the Chemical Society - Dalton Transactions, no. 9, pp. 1431-1438. https://doi.org/10.1039/a800108a

Platinum-catalysed 1,4-diboration of 1,3-dienes. / Clegg, William; Johann, Thorsten R.F.; Marder, Todd B.; Norman, Nicholas C.; Orpen, A. Guy; Peakman, Torren M.; Quayle, Michael J.; Rice, Craig R.; Scott, Andrew J.

In: Journal of the Chemical Society - Dalton Transactions, No. 9, 07.05.1998, p. 1431-1438.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Platinum-catalysed 1,4-diboration of 1,3-dienes

AU - Clegg, William

AU - Johann, Thorsten R.F.

AU - Marder, Todd B.

AU - Norman, Nicholas C.

AU - Orpen, A. Guy

AU - Peakman, Torren M.

AU - Quayle, Michael J.

AU - Rice, Craig R.

AU - Scott, Andrew J.

PY - 1998/5/7

Y1 - 1998/5/7

N2 - The chiral diborane(4) compounds B2[R,R-O2CH(CO2Me)CH(CO2Me)] 2, B2(S,O2CH2CHPh)2, B2(R,R-O2-CHPhCHPh)2 and B2(O2C20H12)2 (O2C20H12 = 1,7′-bi-2-naphtholate) have been synthesized. All four compounds have been characterised by X-ray crystallography, the latter as a racemate. The B-B bond oxidativeaddition reactions of the first three compounds with [Pt(PPh3)2(μ-C2H4)] resulted in the platinum(II) bis(boryl) complexes cis-[Pt(PPh3)2{B[R,R-O2CH(CO 2Me)CH(CO2Me)]}2], cis-[Pt(PPh3)2{B(S-O2CH2CHPh)} 2] and cis-[Pt(PPh3)2{B(R,R-O2CHPhCHPh)}2]; the former two were also characterised by X-ray crystallography. The platinum-catalysed diborations of a range of prochiral 1,3-dienes with the compounds B2[R,R-O2CH(CO2Me)-CH(CO2Me)] 2, B2(S-O2CH2CHPh)2 and B2(R,R-O2CHPhCHPh)2 were studied. Although these reactions were clean and quantitative, observed product d.e.s (measured by 1H NMR spectroscopy) were low or non-existent indicating that chirality transfer from the diborane(4) diolate groups to the diene diboration product is not efficient in these cases.

AB - The chiral diborane(4) compounds B2[R,R-O2CH(CO2Me)CH(CO2Me)] 2, B2(S,O2CH2CHPh)2, B2(R,R-O2-CHPhCHPh)2 and B2(O2C20H12)2 (O2C20H12 = 1,7′-bi-2-naphtholate) have been synthesized. All four compounds have been characterised by X-ray crystallography, the latter as a racemate. The B-B bond oxidativeaddition reactions of the first three compounds with [Pt(PPh3)2(μ-C2H4)] resulted in the platinum(II) bis(boryl) complexes cis-[Pt(PPh3)2{B[R,R-O2CH(CO 2Me)CH(CO2Me)]}2], cis-[Pt(PPh3)2{B(S-O2CH2CHPh)} 2] and cis-[Pt(PPh3)2{B(R,R-O2CHPhCHPh)}2]; the former two were also characterised by X-ray crystallography. The platinum-catalysed diborations of a range of prochiral 1,3-dienes with the compounds B2[R,R-O2CH(CO2Me)-CH(CO2Me)] 2, B2(S-O2CH2CHPh)2 and B2(R,R-O2CHPhCHPh)2 were studied. Although these reactions were clean and quantitative, observed product d.e.s (measured by 1H NMR spectroscopy) were low or non-existent indicating that chirality transfer from the diborane(4) diolate groups to the diene diboration product is not efficient in these cases.

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DO - 10.1039/a800108a

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Clegg W, Johann TRF, Marder TB, Norman NC, Orpen AG, Peakman TM et al. Platinum-catalysed 1,4-diboration of 1,3-dienes. Journal of the Chemical Society - Dalton Transactions. 1998 May 7;(9):1431-1438. https://doi.org/10.1039/a800108a