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Review
. 2016 Nov 21;21(11):1573.
doi: 10.3390/molecules21111573.

Chiral Hypervalent, Pentacoordinated Phosphoranes

Dorota Krasowska  1 , Jacek Chrzanowski  2 , Piotr Kiełbasiński  3 , Józef Drabowicz  4   5
Affiliations
Review

Chiral Hypervalent, Pentacoordinated Phosphoranes

Dorota Krasowska et al. Molecules. .

Abstract

This review presents synthetic procedures applied to the preparation of chiral (mainly optically active) pentacoordinated, hypervalent mono and bicyclic phosphoranes. The mechanisms of their stereoisomerization and their selected interconversions are also presented.

Keywords: Berry pseudorotation; chirality; hypervalency; phosphoranes; turnstile rotation.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
General formula of a phosphorus-containing trigonal bipyramid.
Figure 2
Figure 2
Resonance structure of phosphonium ylides.
Figure 3
Figure 3
Chiral and achiral structure of hypervalent phosphoranes.
Scheme 1
Scheme 1
Berry pseudorotation mechanism.
Scheme 2
Scheme 2
“Turnstile” rotation mechanism (TR).
Scheme 3
Scheme 3
Possible mechanism for nucleophilic substitution reaction at phosphorus.
Scheme 4
Scheme 4
The rearrangement of the lithium salts 2a–c derived from the 2-bromophenylphosphinite boranes 1a–c to the o-hydroxyphenylphosphine boranes 3a–c.
Scheme 5
Scheme 5
Stereochemical outcome of the regiospecific ring opening reaction of the diastereomerically pure dioxaphospholane borane 4 with organolithium reagents.
Scheme 6
Scheme 6
The hydrolysis of quasiphosphonium salts 8a and 8b involving two hydroxyphosphorane intermediates 10a and 10b.
Scheme 7
Scheme 7
The intramolecular transesterification of the 2-hydroxyphenyl phosphite 11.
Scheme 8
Scheme 8
Reaction of cyclic oxaphospholane 14 and Grignard reagents.
Scheme 9
Scheme 9
Monocyclic halophosphoranes 19.
Scheme 10
Scheme 10
Reaction of cyclic phosphite 20 with dimethyl acetylenedicarboxylate.
Scheme 11
Scheme 11
Reaction of ylide 22 with hexafluoroacetone.
Scheme 12
Scheme 12
Reaction of ylide 24 with hexafluoroacetone.
Scheme 13
Scheme 13
Reaction of organophosphorus derivatives 26a–c with hexafluoroacetone.
Scheme 14
Scheme 14
Preparation of monocyclic halophosphoranes 31a–e.
Scheme 15
Scheme 15
Preparation of monocyclic (ethylthio)fluorophosphorane 34.
Scheme 16
Scheme 16
Preparation of enantiomeric spirophosphoranes 38.
Scheme 17
Scheme 17
Preparation of 38 using biphenyl-biphenylyl-2-phosphine 39.
Scheme 18
Scheme 18
Reaction of spirocyclotetraalkylphosphonium salts 41 with a series of organolithium reagents.
Scheme 19
Scheme 19
Reaction of biphenylphenylethylidene-phosphonium ylide 43 with benzaldehydes.
Scheme 20
Scheme 20
Synthesis of 1,2-Azaphosphetidine 47 and 48.
Scheme 21
Scheme 21
The equilibrium between phosphoranes 47 and 49.
Scheme 22
Scheme 22
Thermolysis of 47 or 48.
Scheme 23
Scheme 23
Cycloaddition reaction of the iminophosphorane 50 with an alkyne.
Scheme 24
Scheme 24
Synthesis of spiro-oxaphosphetanes 54–58 and their thermal decompositions.
Scheme 25
Scheme 25
Synthesis of diastereomeric phosphoranes 60 and enantiomeric phosphoranes 61.
Scheme 26
Scheme 26
Conversion of phosphoranes 61 to esters 62.
Scheme 27
Scheme 27
Synthesis of diastereomeric phosphoranes 64.
Scheme 28
Scheme 28
Conversion of diastereomeric phosphoranes 64 to enantiomeric phosphoranes 59.
Scheme 29
Scheme 29
Synthesis of (O-cis) spirophosphoranes 66 and their stereomutation to (O-trans) phosphoranes 67.
Scheme 30
Scheme 30
Reactivity of O-cis-66b and O-trans-67b toward nucleophiles.
Scheme 31
Scheme 31
Reaction of phosphoranide 70 with silane 71.
Scheme 32
Scheme 32
Reactivity of phosphoranes 59, 61 and 73.
Scheme 33
Scheme 33
Synthesis of phosphoranes 76 and 77.
Scheme 34
Scheme 34
Synthesis of phosphoranes 76 and their interconversion into 77.
Scheme 35
Scheme 35
Methyllithium induced epimerization of O-equatorial methylphosphorane 76a.
Scheme 36
Scheme 36
Synthesis of phosphorane derivatives 78 and/or 79.
Scheme 37
Scheme 37
Synthesis of isomeric mixture of oxaphosphetane 80a and 80b.
Scheme 38
Scheme 38
Reaction of phosphirenes 81a and 81b with o-chloranil.
Scheme 39
Scheme 39
Reactions of monocyclic phosphorus ylide 84.
Scheme 40
Scheme 40
Syntheses of bicyclic phosphoranes 90–93.
Scheme 41
Scheme 41
Thermolysis of spirophosphorane 90c.
Scheme 42
Scheme 42
The mechanism of formation of the bicyclic phosphorane 93 from cyclic iminophosphinate 89.
Scheme 43
Scheme 43
Synthesis of pentacoordinate phosphorane 99 and phosphinate derivative 100.
Scheme 44
Scheme 44
Synthesis of aminophosphoranes 102 and 103.
Scheme 45
Scheme 45
Reactions of cyclic five or six-membered tricoordinated phosphorus compounds with 2-hydroxy-5-nitrobenzyl halides.
Scheme 46
Scheme 46
Synthesis of bicyclic aminophosphoranes 112.
Scheme 47
Scheme 47
Synthesis of bicyclic aminophosphorane 114.
Scheme 48
Scheme 48
The mechanism for the formation of spirophosphorane 114.
Scheme 49
Scheme 49
Syntheses of bicyclic diaminophosphoranes 117 and 118.
Scheme 50
Scheme 50
Synthesis of bicyclic diaminophosphorane 120.
Scheme 51
Scheme 51
Syntheses of bicyclic diaminophosphoranes 121 and 122.
Scheme 52
Scheme 52
Synthesis of bicyclic diaminophosphoranes 122.
Scheme 53
Scheme 53
Synthesis of bicyclic phosphoranes 127.
Scheme 54
Scheme 54
Synthesis of bicyclic phosphorane 132.
Scheme 55
Scheme 55
Synthesis of bicyclic azaphosphoranes 135.
Scheme 56
Scheme 56
Synthesis of hydrospirophosphoranes 137 and 138 derived from l-amino acids.
Scheme 57
Scheme 57
Preparation of pentacoordinate spirophosphorane carbamates 139.
Scheme 58
Scheme 58
The mechanism of formation spirophosphorane carbamates 139.
Scheme 59
Scheme 59
Synthesis of pentacoordinate pyrospirophosphoranes 141–143.
Scheme 60
Scheme 60
Synthesis of alkoxy spirophosphoranes 144,145.
Scheme 61
Scheme 61
Syntheses of bicyclic hydrophosphoranes 147–149 and their use as chiral ligands.
Scheme 62
Scheme 62
Chiral triquinphosphoranes 152–154 and their reactions with various activated carbonyl compounds.
Scheme 63
Scheme 63
Reaction of chiral hydrido-triquinphosphorane 158 with alkyl disulfides.
Scheme 64
Scheme 64
Syntheses of bicyclic hydrophosphoranes 163–165.
Scheme 65
Scheme 65
Syntheses of bicyclic hydrophosphoranes 163 and 165.
Scheme 66
Scheme 66
Synthesis of bicyclic hydrophosphoranes 164 and 170.
Scheme 67
Scheme 67
Synthesis of bicyclic spirophosphoranes 173 and 175.
Scheme 68
Scheme 68
Synthesis of bicyclic phosphoranes 177.
Scheme 69
Scheme 69
Synthesis of oligopeptides with the use of spirophosphoranes 177 as substrates.
Scheme 70
Scheme 70
Interconversions of spirophosphoranes 181 and 182.
Scheme 71
Scheme 71
Preparation of chiral metallophosphoranes 192.
Scheme 72
Scheme 72
Functionalization of hydrophosphorane 193 leading to phosphoranes 196 and 198–200.
Scheme 73
Scheme 73
Alkylation of metallophosphoranes 196.
Scheme 74
Scheme 74
Oxidation of hydrophosphorane 202.
Scheme 75
Scheme 75
Formation of salt 205.
Scheme 76
Scheme 76
Synthesis of spirophosphoranes 207 and 210.
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