Online citations, reference lists, and bibliographies.
← Back to Search

Synthesis Of P-stereogenic Compounds Via Kinetic Deprotonation And Dynamic Thermodynamic Resolution Of Phosphine Sulfides: Opposite Sense Of Induction Using (-)-sparteine.

Jonathan J. Gammon, V. Gessner, G. Barker, Johan Granander, A. Whitwood, C. Strohmann, P. O'Brien, B. Kelly
Published 2010 · Chemistry, Medicine

Cite This
Download PDF
Analyze on Scholarcy
Share
A systematic study of the asymmetric deprotonation of a dimethyl-substituted phosphine sulfide using organolithium bases in the presence of (-)-sparteine has been carried out. Use of nBuLi and (-)-sparteine in Et(2)O at -78 °C gave trapped adducts in ∼88:12 er via a kinetically controlled process that was successfully predicted using a computational approach at the B3LYP/6-31+G(d) level. This initial kinetic enantioselectivity could be enhanced up to 97:3 er by trapping the lithiated intermediate with a prochiral electrophile (e.g., pivaldehyde or tBuPCl(2)). In addition, it was found that the R(P) and S(P) stereoisomers of the lithiated methylphosphine sulfide could interconvert at temperatures above 0 °C. Such interconversion is unprecedented and differs from the configurational instability of organolithiums that are stereogenic at a lithiated carbon atom. The major, thermodynamically preferred diastereomeric (-)-sparteine-complexed lithated phosphine sulfide was investigated by X-ray crystallography and computational methods at the B3LYP/6-31+G(d) level. Through the interconversion of the R(P) and S(P) stereoisomers of the lithiated methylphosphine sulfide, a novel dynamic thermodynamic resolution of a racemic lithiated phosphine sulfide has been developed. Thus, the phosphine sulfide was lithiated with nBuLi, and then (-)-sparteine was added. After equilibration at 0 °C for 3 h, electrophilic trapping generated an adduct in 81:19 er with the configuration opposite to that obtained under kinetic control. Thus, the methodology provides access to P-stereogenic compounds with the opposite sense of induction using (-)-sparteine as the ligand simply by changing the reaction conditions (kinetic or thermodynamic control).
This paper references
10.1039/B408509D
Highly enantioselective reaction of lithiated N-Boc-thiazolidine: a new chiral formyl anion equivalent.
L. Wang (2004)
10.1021/OM050872F
Studies of Complexes between Phenyllithium and (−)-Sparteine in Ether Solutions
R. Sott (2006)
10.1002/1521-3773(20020301)41:5<716::AID-ANIE716>3.0.CO;2-Z
Configurational stability and transfer of stereochemical information in the reactions of enantioenriched organolithium reagents.
A. Basu (2002)
10.1021/JA00140A028
ENANTIOSELECTIVE DEPROTONATION AS A VEHICLE FOR THE ASYMMETRIC SYNTHESIS OF C2-SYMMETRIC P-CHIRAL DIPHOSPHINES
Alexander R. Muci (1995)
10.1002/EJOC.200400006
Desymmetrization of Prochiral Phosphanes Using Derivatives of (−)-Cytisine
M. Johansson (2004)
10.1021/JO990131M
Methylene-Bridged P-Chiral Diphosphines in Highly Enantioselective Reactions.
Y. Yamanoi (1999)
10.1021/JA053458F
An air-stable P-chiral phosphine ligand for highly enantioselective transition-metal-catalyzed reactions.
T. Imamoto (2005)
10.1021/JA062616F
Catalytic asymmetric synthesis of ferrocenes and P-stereogenic bisphosphines.
Cédric Genet (2006)
10.1021/JA973423I
P-CHIRAL BIS(TRIALKYLPHOSPHINE) LIGANDS AND THEIR USE IN HIGHLY ENANTIOSELECTIVE HYDROGENATION REACTIONS
T. Imamoto (1998)
10.1021/ol901977p
Regioselective lithiation of silyl phosphine sulfides: asymmetric synthesis of P-stereogenic compounds.
Jonathan J. Gammon (2009)
10.1002/chem.200903059
Asymmetric substitutions of 2-lithiated N-boc-piperidine and N-Boc-azepine by dynamic resolution.
I. Coldham (2010)
10.1039/b810988e
Dynamic resolution of N-Boc-2-lithiopiperidine.
I. Coldham (2008)
10.1002/1615-4169(20010129)343:1<118::AID-ADSC118>3.0.CO;2-Z
Asymmetric Hydrogenation Catalyzed by (S,S)-R-BisP*-Rh and (R,R)-R-MiniPHOS Complexes: Scope, Limitations, and Mechanism
I. Gridnev (2001)
10.1021/AR000077S
Dynamic thermodynamic resolution: control of enantioselectivity through diastereomeric equilibration.
P. Beak (2000)
10.1021/JA951895W
CONTROL OF THE ENANTIOCHEMISTRY OF ELECTROPHILIC SUBSTITUTIONS OF N-PIVALOYL-ALPHA -LITHIO-O-ETHYLANILINE : STEREOINFORMATION TRANSFER BASED ON THE ME THOD OF ORGANOLITHIUM FORMATION
A. Basu (1996)
10.1002/ANIE.199521581
Generation of Enantiomerically Enriched Lithium Indenides by Means of (–)‐Sparteine: Structure, Stereoselective Substitution, and Solvent Effects
I. Hoppe (1995)
10.1002/ANIE.198900691
Asymmetric Homoaldol Reaction by Enantioselective Lithiation of a Prochiral 2‐Butenyl Carbamate
D. Hoppe (1989)
10.1021/JA973685K
A Direct Synthesis of P-Chiral Phosphine−Boranes via Dynamic Resolution of Lithiated Racemic tert-Butylphenylphosphine−Borane with (−)-Sparteine
B. Wolfe (1998)
10.1021/JA027774V
A readily-accessible (+)-sparteine surrogate.
Michael J. Dearden (2002)
10.1002/1521-3773(20020503)41:9<1612::AID-ANIE1612>3.0.CO;2-H
A chiral 1,2-bisphospholane ligand with a novel structural motif: applications in highly enantioselective Rh-catalyzed hydrogenations.
Wenjun Tang (2002)
10.1021/JA0675144
An experimental and computational study of stereoselectivity and reactivity in Lewis acid promoted lithiation-substitution of tertiary amines.
S. V. Kessar (2007)
10.1002/ANIE.200390251
Phospholane-oxazoline ligands for Ir-catalyzed asymmetric hydrogenation.
Wenjun Tang (2003)
10.1021/OM0494871
Crystal structures of (+)-sparteine surrogate adducts of methyllithium and phenyllithium
C. Strohmann (2004)
10.1021/JA057348K
Crystal structures of the chiral lithiosilanes [(Lis)-PhMe2SiLi x THF x (-)-sparteine] and [Ph2(NEt2)SiLi x (-)-sparteine].
C. Strohmann (2006)
10.1021/JA00460A018
Asymmetric hydrogenation. Rhodium chiral bisphosphine catalyst
B. D. Vineyard (1977)
10.1021/JA00062A079
Solution- and solid-state structure and dynamics of thiophosphonamide anions: electronic tuning of rotational barriers
S. Denmark (1993)
10.1002/9783906390628.CH3
Overview of Carbanion Dynamics and Electrophilic Substitutions in Chiral Organolithium Compounds.
R. E. Gawley (2010)
10.1039/B711420F
Basic instinct: design, synthesis and evaluation of (+)-sparteine surrogates for asymmetric synthesis.
P. O’Brien (2008)
10.1021/JA061963M
Dynamic thermodynamic and dynamic kinetic resolution of 2-lithiopyrrolidines.
I. Coldham (2006)
10.1002/9783906390628.CH7
Dynamic Resolutions of Chiral Organolithiums
I. Coldham (2010)
10.1002/(SICI)1521-3765(19991203)5:12<3464::AID-CHEM3464>3.0.CO;2-Q
Experimental and Theoretical Investigations of Lithio‐Indenyl Carbamate/(−)‐Sparteine and (−)‐α‐Isosparteine Complexes
T. Heinl (1999)
10.1002/ANIE.200351308
[tBuLi.(-)-sparteine]: molecular structure of the first monomeric butyllithium compound.
C. Strohmann (2003)
10.1002/ANIE.200604978
Stereo- and regiochemical divergence in the substitution of a lithiated alk-1-en-3-yn-2-yl carbamate: synthesis of highly enantioenriched vinylallenes or alk-3-en-5-yn-1-ols.
Roland Bou Chedid (2007)
10.1021/JA970930R
Two Different Pathways of Stereoinformation Transfer: Asymmetric Substitutions in the (−)-Sparteine Mediated Reactions of Laterally Lithiated N,N-Diisopropyl-o-ethylbenzamide and N-Pivaloyl-o-ethylaniline
S. Thayumanavan (1997)
10.1021/OM050794W
Crystal Structures of [PhLi·(−)-sparteine]2, [PhOLi·(−)-sparteine]2, and the Mixed Aggregate [PhLi·PhOLi·2(−)-sparteine]
C. Strohmann (2006)
10.1039/b806864j
Catalytic asymmetric deprotonation of phosphine boranes and sulfides as a route to P-stereogenic compounds.
Jonathan J. Gammon (2008)
10.1039/c0cc00130a
Unexpected direct dilithiation of a prochiral phosphine borane.
V. Gessner (2010)
10.1021/JA056026D
Catalytic asymmetric deprotonation using a ligand exchange approach.
M. McGrath (2005)
10.1021/CR020049I
New chiral phosphorus ligands for enantioselective hydrogenation.
Wenjun Tang (2003)
10.1002/1521-3773(20021018)41:20<3887::AID-ANIE3887>3.0.CO;2-J
Enantioselective synthesis of substituted pyrrolidines by dynamic resolution.
I. Coldham (2002)
10.1002/ANIE.200501142
Solid-state structure and enantioselective reactions of a complex of a 1-thio-substituted propargyllithium and (-)-sparteine.
R. Otte (2005)
10.1016/J.TETASY.2010.03.025
Improved synthetic routes to methylene-bridged P-chiral diphosphine ligands via secondary phosphine–boranes
T. Imamoto (2010)



This paper is referenced by
10.1002/ANGE.201205465
ortho‐ und meta‐Magnesierung von funktionalisierten Anilinen und aminosubstituierten Pyridinen und Pyrazinen bei Raumtemperatur
G. Monzón (2012)
10.1016/B978-0-08-095167-6.00317-7
3.17 Synthetically Derived Auxiliaries: Phosphorus Derivatives
S. Jugé (2012)
10.1021/ol400971q
Directed ortho-lithiation of aminophosphazenes: an efficient route to the stereoselective synthesis of P-chiral compounds.
M. Casimiro (2013)
10.1007/978-3-319-15473-2
Phosphorus Chemistry I: Asymmetric Synthesis and Bioactive Compounds
Jean-Luc Montchamp (2015)
10.1002/chem.201502647
Stereospecific Synthesis of α- and β-Hydroxyalkyl P-Stereogenic Phosphine-Boranes and Functionalized Derivatives: Evidence of the P=O Activation in the BH3 -Mediated Reduction.
Sébastien Lemouzy (2015)
10.1002/ejoc.202000406
Introducing Chirality at Phosphorus Atoms: An Update on the Recent Synthetic Strategies for the Preparation of Optically Pure P‐Stereogenic Molecules
Sébastien Lemouzy (2020)
10.1021/cr400307e
(-)-Cytisine and derivatives: synthesis, reactivity, and applications.
J. Rouden (2014)
10.1021/acs.joc.7b01767
Intramolecular Nucleophilic Substitution of ω-Haloalkylphosphine Derivatives.
P. Woźnicki (2017)
10.1002/ANGE.201409165
Stereoselektive Synthese und Reaktionen von in Position 3 funktionalisierten sekundären Alkyllithiumverbindungen
Kohei Moriya (2015)
10.1021/ja2034816
Bulky, optically active P-stereogenic phosphine-boranes from pure H-menthylphosphinates.
David Gatineau (2011)
10.1021/ja312352p
Efficient asymmetric synthesis of P-chiral phosphine oxides via properly designed and activated benzoxazaphosphinine-2-oxide agents.
Z. Han (2013)
10.1039/c4ob01574f
Addition of optically pure H-phosphinate to ketones: selectivity, stereochemistry and mechanism.
Yong-ming Sun (2014)
10.1002/chem.201204076
Preparation of stereodefined secondary alkyllithium compounds.
S. Seel (2013)
10.1002/anie.201308679
Diastereoselective synthesis of open-chain secondary alkyllithium compounds and trapping reactions with electrophiles.
Guillaume Dagousset (2014)
10.1002/ANGE.201303650
Katalytische, stereoselektive ortho‐Lithiierung eines Ferrocenderivats
P. Steffen (2013)
10.1021/jacs.5b04415
Hammond Postulate Mirroring Enables Enantiomeric Enrichment of Phosphorus Compounds via Two Thermodynamically Interconnected Sequential Stereoselective Processes.
K. V. Rajendran (2015)
10.1039/c6dt00995f
Ruthenium complexes of P-stereogenic phosphines with a heterocyclic substituent.
P. Clavero (2016)
10.1021/acs.orglett.5b00122
Asymmetric Synthesis of P-Stereogenic Phosphinic Amides via Pd(0)-Catalyzed Enantioselective Intramolecular C-H Arylation.
L. Liu (2015)
10.1016/J.TETASY.2012.01.007
Recent developments in the asymmetric synthesis of Р-chiral phosphorus compounds
O. I. Kolodiazhnyi (2012)
10.1002/ejoc.201901475
P‐Stereogenic Phosphonates via Dynamic Kinetic Resolution: A Route towards Enantiopure Tertiary Phosphine Oxides
Aabid Mohd (2019)
10.1002/anie.201409165
Stereoselective synthesis and reactions of secondary alkyllithium reagents functionalized at the 3-position.
Kohei Moriya (2015)
10.1016/J.TETLET.2015.05.006
Asymmetric synthesis of diarylmethane derivatives by dynamic kinetic resolution
Lewis M. Gooch (2015)
10.1021/ol202916j
Enantioselective preparation of P-chiral phosphine oxides.
H. Adams (2011)
10.1039/c1dt10058k
Synthesis and structural chemistry of alkali metal tris(HMDS) magnesiates containing chiral diamine donor ligands.
P. García-Álvarez (2011)
10.1002/9783527667512.CH2
Computational Perspectives on Organolithiums
Nilsson Lill (2014)
10.1080/00268976.2011.647103
Selectivity in the aggregates of the chiral organolithium N-Boc-2-lithiopiperidine with a chiral ligand: a DFT study
H. Ince (2012)
10.1016/B978-0-08-095167-6.00320-7
3.20 Stoichiometric Auxiliary Ligands for Metals and Main Group Elements: Ligands for Lithium
K. Tomioka (2012)
10.1002/chem.201601911
Stereoselective Synthesis and Retentive Trapping of α-Chiral Secondary Alkyllithiums Leading to Stereodefined α,β-Dimethyl Carboxylic Esters.
V. Morozova (2016)
10.1021/ol503371r
One-pot process that efficiently generates single stereoisomers of 1,3-bisphosphinylpropanes having five chiral centers.
H. Zhang (2015)
10.1039/c7cc02263h
Efficient synthesis of cyclic P-stereogenic phosphinamides from acyclic chiral precursors via radical oxidative intramolecular aryl C-H phosphinamidation.
Y. Chen (2017)
10.1039/c2cc34136k
Identification of a key intermediate in the asymmetric Appel process: one pot stereoselective synthesis of P-stereogenic phosphines and phosphine boranes from racemic phosphine oxides.
K. V. Rajendran (2012)
10.1002/asia.201301650
Stereogenic phosphorus-induced diastereoselective formation of chiral carbon during nucleophilic addition of chiral H-P species to aldehydes or ketones.
H. Zhang (2014)
See more
Semantic Scholar Logo Some data provided by SemanticScholar