Regioselectivity and memory effects in palladium catalyzed allylic alkylations with bidentate P^PS donor ligands

Milheiro, Suzanna C.; Faller, J. W.

doi:10.1016/j.jorganchem.2010.10.022

“…This atom‐efficient reaction enables the facile preparation of a Pd complex bearing a BPMS ligand,– such as 16 aj , without the need for BPMS purification (Figure ). When a mixture of diphosphane monosulfide 4 a and alkene 2 j was photoirradiated, BPMS 8 aj was obtained in 92 % yield.…”

Section: Resultsmentioning

confidence: 99%

“…Recently,o rganophosphanes with as oft Lewis base center (P III )a nd ar elatively hard one [P V (S)] at the vicinalp ositions have been used as hemilabile P, S-bidentate ligandsi nt ransition-metal-catalyzed reactions. [11] Furthermore, phosphane sul-fides are easily reducedt oa fford bidentate bis-phosphane ligands.T herefore, the 1,2-adducts of diphosphane monosulfides are themselves useful andp romising ligands as well as valuablep recursors for bidentateb is-phosphane ligands. Hence, we focusedonthe high reactivity of diphosphane monosulfidest oward alkenes and investigated this thiophosphorylphosphanation process in detail.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Bis(phosphanyl)alkane Monosulfides by the Addition of Diphosphane Monosulfides to Alkenes under Light

Sato

¹

,

Kawaguchi

²

,

Nomoto

³

et al. 2019

Chemistry A European J

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Bis‐phosphanated compounds are regarded as the most ubiquitous privileged ligand structures in transition‐metal catalysis. The development of highly atom economical reactions is of great importance for their syntheses because less atom economical methods often require complicated purification procedures under inert atmospheres to remove excess starting materials and byproducts. Herein, the photoinduced addition reactions of diphosphane monosulfides bearing PV(S)−PIII single bonds to alkenes is disclosed. These reactions require only equimolar amounts of the diphosphane monosulfide relative to the alkene and facilitate highly selective introduction of two different types of phosphorus‐containing groups, such as thiophosphoryl and phosphanyl groups, into a variety of alkenes without any catalyst, base, or additive.

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“…That means that unlike our previous findings, linear allyl amino boronates are not formed through a branched-to-linear isomerization. Furthermore, to rule out potential memory effects causing the linear regioselectivity, [59][60][61][62][63] we carried out the allylic amination utilizing linear acetate 3 and observed identical selectivity for the formation of 7b (Scheme 5). When alkyl zincate nBuZnCl•LiCl was utilized, we did not observe the desired alkylated product.…”

Section: P1-ts2mentioning

confidence: 99%

DABN Borazabicycles: Formation from MIDA Boronates and Synthetic Utility

Kaldas¹,

Tien²,

Gomes³

et al. 2020

Preprint

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<div> <div> <div> <p>We report that coordinative hemilability allows the MIDA amine to behave as a nucleophile to intercept π-allyl intermediates. A mechanistic investigation indicates that this rearrangement proceeds through an SN2-like displacement at tetrasubstituted boron to furnish novel DABN (2,8- dioxa-5-aza-1-borabicyclo[3.3.1]nonane-3,7-dione) boronates. Oxidative addition into the N-C bond of the DABN scaffold reverses the reaction and furnishes borylated π-allyl intermediates that can then be trapped with complete linear selectivity. DFT calculations indicate that stabilizing interactions in the transition state, as well as the steric bulk of the MIDA unit, are the origins of the excellent regioselectivity. We further demonstrate the utility of our new reagents by way of a 3-component coupling that features allylammonium DABN boronates as linchpin reagents. This report disseminates a previously unknown aspect of MIDA boronates that can now be exploited. </p> </div> </div> </div>

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“…That means that unlike our previous findings, linear allyl amino boronates are not formed through a branched-to-linear isomerization. Furthermore, to rule out potential memory effects causing the linear regioselectivity, [59][60][61][62][63] we carried out the allylic amination utilizing linear acetate 3 and observed identical selectivity for the formation of 7b (Scheme 5).…”

Section: P1-ts2mentioning

confidence: 99%

DABN Borazabicycles: Formation from MIDA Boronates and Synthetic Utility

Kaldas¹,

Tien²,

Gomes³

et al. 2020

Preprint

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<div> <div> <div> <p>We report that coordinative hemilability allows the MIDA amine to behave as a nucleophile to intercept π-allyl intermediates. A mechanistic investigation indicates that this rearrangement proceeds through an SN2-like displacement at tetrasubstituted boron to furnish novel DABN (2,8- dioxa-5-aza-1-borabicyclo[3.3.1]nonane-3,7-dione) boronates. Oxidative addition into the N-C bond of the DABN scaffold reverses the reaction and furnishes borylated π-allyl intermediates that can then be trapped with complete linear selectivity. DFT calculations indicate that stabilizing interactions in the transition state, as well as the steric bulk of the MIDA unit, are the origins of the excellent regioselectivity. We further demonstrate the utility of our new reagents by way of a 3-component coupling that features allylammonium DABN boronates as linchpin reagents. This report disseminates a previously unknown aspect of MIDA boronates that can now be exploited. </p> </div> </div> </div>

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Regioselectivity and memory effects in palladium catalyzed allylic alkylations with bidentate P^PS donor ligands

Cited by 14 publications

References 60 publications

Synthesis of Bis(phosphanyl)alkane Monosulfides by the Addition of Diphosphane Monosulfides to Alkenes under Light

Synthesis of Bis(phosphanyl)alkane Monosulfides by the Addition of Diphosphane Monosulfides to Alkenes under Light

DABN Borazabicycles: Formation from MIDA Boronates and Synthetic Utility

DABN Borazabicycles: Formation from MIDA Boronates and Synthetic Utility

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