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Review
. 2017 Nov 4;22(11):1901.
doi: 10.3390/molecules22111901.

First-Row Late Transition Metals for Catalytic Alkene Hydrofunctionalisation: Recent Advances in C-N, C-O and C-P Bond Formation

Sophie Bezzenine-Lafollée  1 , Richard Gil  2 , Damien Prim  3 , Jérôme Hannedouche  4   5
Affiliations
Review

First-Row Late Transition Metals for Catalytic Alkene Hydrofunctionalisation: Recent Advances in C-N, C-O and C-P Bond Formation

Sophie Bezzenine-Lafollée et al. Molecules. .

Abstract

This review provides an outline of the most noteworthy achievements in the area of C-N, C-O and C-P bond formation by hydroamination, hydroalkoxylation, hydrophosphination, hydrophosphonylation or hydrophosphinylation reaction on unactivated alkenes (including 1,2- and 1,3-dienes) promoted by first-row late transition metal catalytic systems based on manganese, iron, cobalt, nickel, copper and zinc. The relevant literature from 2009 until mid-2017 has been covered.

Keywords: alcohols; amines; first-row late transition metals; hydrofunctionalisation; phosphorus compounds; unactivated alkenes.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Anti-Markovnikov manganese-mediated hydrophosphination of 4-chlorostyrene.
Scheme 2
Scheme 2
Iron-catalysed cyclohydroamination of primary amines tethered to unactivated alkenes.
Scheme 3
Scheme 3
Markovnikov regioselective iron-catalysed electrophilic amination of functionalised vinylarenes.
Scheme 4
Scheme 4
Iron-hydride promoted formal hydroamination of (poly)substituted alkenes and nitro(hetero)arenes.
Scheme 5
Scheme 5
Inter- and intramolecular hydroalkoxylation of alkenes catalysed by iron chloride in the presence of TsOH.
Scheme 6
Scheme 6
Intramolecular hydroalkoxylation of alkenes catalysed by Fe-MMT.
Scheme 7
Scheme 7
FeCl3 catalysed hydroalkoxylation of β-lactam enallenols.
Scheme 8
Scheme 8
FeCl3 catalysed hydroalkoxylation of non β-lactam enallenols.
Scheme 9
Scheme 9
Hydroalkoxylation reaction catalysed by Fe(TFA)3 and Fe(OTs)3 for the synthesis of tetrahydropyrans.
Scheme 10
Scheme 10
Endo/exo-methylene selectivity of intramolecular hydroalkoxylation reaction of allenols catalysed by Fe(OTs)3.
Scheme 11
Scheme 11
Sequential oxidative cyanation/hydroalkoxylation of tertiary N,N-diallylamines catalysed by FeCl2.
Scheme 12
Scheme 12
FeCl2-versus FeCl3-catalysed hydrophosphination of styrene derivatives: a switchable regioselectivity.
Figure 1
Figure 1
β-diketiminate-, salen- or porphyrin-based iron complexes.
Scheme 13
Scheme 13
Anti-Markovnikov hydrophosphination using a salen-based iron complex.
Scheme 14
Scheme 14
Double hydrophosphination of styrenes derivatives promoted by iron complexes.
Scheme 15
Scheme 15
Sequence towards unsymmetrical hydrophosphination of styrene derivatives.
Scheme 16
Scheme 16
Intramolecular hydrophosphination of alkenes promoted by a β-diketiminatoiron(II) complex 8.
Scheme 17
Scheme 17
Cobalt-promoted alkene cyclohydroamidation of N-protected amines.
Scheme 18
Scheme 18
Cobalt-promoted intermolecular hydroalkoxylation of alkenes.
Scheme 19
Scheme 19
Cobalt-promoted intramolecular hydroalkoxylation of alkenyl alcohols.
Scheme 20
Scheme 20
Hydroalkoxylation versus hydroamination promoted by a cobalt complex.
Scheme 21
Scheme 21
Redox switchable hydroalkoxylation of a cobalt complex.
Scheme 22
Scheme 22
Intermolecular hydroalkoxylation of butadiene with primary alcohols catalysed by nickel.
Scheme 23
Scheme 23
Nickel-catalysed hydrophosphinylation of unactivated linear alkenes.
Figure 2
Figure 2
Bidentate diphosphine ligands used in the copper-catalysed hydroamination reactions.
Scheme 24
Scheme 24
Copper (I)-catalysed cyclohydroamination of alkenes.
Scheme 25
Scheme 25
Regioselective copper(II)-catalysed intermolecular hydroamination of terminal allenes.
Scheme 26
Scheme 26
Regio- and enantioselective copper (I) hydride catalysed electrophilic amination of styrene derivatives.
Scheme 27
Scheme 27
Regio- and enantioselective copper (I) hydride catalysed electrophilic amination of styrene derivatives, vinylsilanes and terminal aliphatic alkenes.
Scheme 28
Scheme 28
Regio- and enantioselective copper (I) hydride catalysed electrophilic amination of styrene derivatives for the preparation of chiral secondary amines.
Scheme 29
Scheme 29
Regio- and enantioselective copper (I) hydride catalysed electrophilic amination internal alkenes.
Scheme 30
Scheme 30
Enantioselective and electronically controlled regioselective copper (I) hydride catalysed electrophilic amination of homoallylic esters.
Scheme 31
Scheme 31
Addition of 4-methoxyphenol to isoprene catalysed by a Cu(OTf)2-bipyridine system.
Scheme 32
Scheme 32
Enantioselective intramolecular hydroalkylation of alkenes catalysed by a chiral copper complex.
Scheme 33
Scheme 33
Intramolecular hydroalkoxylation reaction catalysed by mesityl copper (I) in presence of Xantphos or (R)-DTBM-SEGPHOS.
Scheme 34
Scheme 34
Copper-catalysed intramolecular hydroalkoxylation of allenes by a selective 5-endo cyclisation.
Scheme 35
Scheme 35
Copper-catalysed intermolecular hydrophosphination of styrene derivatives.
Scheme 36
Scheme 36
Zinc-catalysed intramolecular alkene hydroamination of primary amines.
Scheme 37
Scheme 37
Zn(OTf)2-catalysed 6-exo-dig cyclisation of γ-allenols.
See this image and copyright information in PMC

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