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Review
. 2022 Mar 21;27(6):2030.
doi: 10.3390/molecules27062030.

Preparation and Synthetic Applications of Five-to-Seven-Membered Cyclic α-Diazo Monocarbonyl Compounds

Daniil Zhukovsky  1 , Dmitry Dar'in  2 , Olga Bakulina  2 , Mikhail Krasavin  2   3
Affiliations
Review

Preparation and Synthetic Applications of Five-to-Seven-Membered Cyclic α-Diazo Monocarbonyl Compounds

Daniil Zhukovsky et al. Molecules. .

Abstract

The reactivity of cyclic α-diazo monocarbonyl compounds differs from that of their acyclic counterparts. In this review, we summarize the current literature available on the synthesis and synthetic applications of three major classes of cyclic α-diazo monocarbonyl compounds: α-diazo ketones, α-diazo lactones and α-diazo lactams.

Keywords: preparation; synthetic applications; α-diazo ketones; α-diazo lactams; α-diazo lactones.

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Conflict of interest statement

The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

Figures

Scheme 1
Scheme 1
Example of deformylative diazo transfer in the synthesis of bicyclic α-diazo ketone 1.
Scheme 2
Scheme 2
Examples of direct diazo transfer reactions not requiring pre-formylation.
Scheme 3
Scheme 3
Synthesis of diazo ketone 4 via trifluoroacetylation.
Scheme 4
Scheme 4
The ‘SAFE’ method of preparing cyclic α-diazo ketones 5.
Scheme 5
Scheme 5
The use of the Bredereck’s reagent (6) in the activation of sensitive substrates.
Scheme 6
Scheme 6
Examples of α-diazo ketone synthesis via oxime (8) and tosyl hydrazone (9) fragmentation.
Scheme 7
Scheme 7
Approaches to the synthesis of β-hydroxy-α-diazo cyclic ketones.
Scheme 8
Scheme 8
Various transformations of 3-diazo camphor under microwave irradiation and conventional heating.
Scheme 9
Scheme 9
The key step in the synthesis of ent-[3]ladderanol.
Scheme 10
Scheme 10
Example of photolytic decomposition of α-diazo cyclopentanone with diastereoselective formation of the Wolff rearrangement product.
Scheme 11
Scheme 11
Photolysis of 4-diazodihydrofuran-3(2H)-ones in the presence of various nucleophiles.
Scheme 12
Scheme 12
The Wolff rearrangement involving six-membered α-diazo carbonyl compounds.
Scheme 13
Scheme 13
Photolysis of bicyclic diazo compound 21 in methanol.
Scheme 14
Scheme 14
Using hexamethyldisylazane as a nucleophile in the Wolff rearrangement.
Scheme 15
Scheme 15
Examples of an enantioselective nucleophile addition to ketenes.
Scheme 16
Scheme 16
Enantioselective synthesis of (+)-psiguadial B (24).
Scheme 17
Scheme 17
Bis-diazo compound photolysis in the synthesis of iso[1.1.1.1]pagodane 27.
Scheme 18
Scheme 18
Synthesis of [4.4.4.5]fenestrane skeleton.
Scheme 19
Scheme 19
Synthesis of Dewar arene structures.
Scheme 20
Scheme 20
Photochemical production of strongly luminescent rhodamine B derivatives.
Scheme 21
Scheme 21
Rhodamine–fluoresceine sensor for esterases.
Scheme 22
Scheme 22
Enantioselective, Pd(II)-catalyzed formation of spirocyclic adduct 34.
Scheme 23
Scheme 23
Cyclic ketenes in [2 + 2] cycloaddition reactions.
Scheme 24
Scheme 24
The Baeyer–Villiger oxidation of spirocyclic Wolff rearrangement products.
Scheme 25
Scheme 25
Decomposition of 3-diazodihydrofuran-3(2H)-ones 39 in trifluoroacetic acid.
Scheme 26
Scheme 26
Mechanism of decomposition of 39 in trifluoroacetic acid.
Scheme 27
Scheme 27
Tin(II) chloride catalyzed Tiffeneau–Demjanov rearrangement of 42.
Scheme 28
Scheme 28
Rh(II)-catalyzed Tiffeneau–Demjanov rearrangement towards cage products.
Scheme 29
Scheme 29
Rh(II)-catalyzed transformations of substrates 46.
Scheme 30
Scheme 30
The influence of electronic and ring-size factors on the outcome of the Rh(II)-catalyzed rearrangement of α-diazocarbonyl compounds.
Scheme 31
Scheme 31
Transformations of diazo compounds 56 under silver triflate catalysis.
Scheme 32
Scheme 32
Examples of biologically active compounds comprising a 5-alkylidene-2-cyclopentenone scaffold.
Scheme 33
Scheme 33
Example of chirality transfer from diazo substrates 59.
Scheme 34
Scheme 34
Sn(IV) chloride promoted fragmentation of bicyclic β-hydroxy-α-diazo-γ-silyloxy ketones 61.
Scheme 35
Scheme 35
Mechanism of Sn(IV) chloride promoted fragmentation of 61.
Scheme 36
Scheme 36
General metal carbene X-H insertion reactions.
Scheme 37
Scheme 37
Cu(acac)2 catalyzed selective O-H insertion into Boc-protected glycine.
Scheme 38
Scheme 38
Allylic O-H insertions accompanied by sigmatropic rearrangements.
Scheme 39
Scheme 39
Examples of oxonium ylide interception by an electrophilic fluorine or trifluoromethyl group.
Scheme 40
Scheme 40
Example of oxonium ylide interception by an electrophilic SCF3.
Scheme 41
Scheme 41
An example of S-H insertion of Rh(II) carbene derived from a cyclic α-diazo ketone.
Scheme 42
Scheme 42
An example of enantioselective Si-H Rh(II) carbene insertion.
Scheme 43
Scheme 43
Cascade transformation leading to indole derivative 71.
Scheme 44
Scheme 44
Rh(II)-catalyzed reactions of α-diazo cyclopentanone.
Scheme 45
Scheme 45
Carbene insertion into S-Cl bond and subsequent transformations.
Scheme 46
Scheme 46
Examples of carbene insertion into Se-Hal bonds.
Scheme 47
Scheme 47
The Staudinger reaction of 4-diazotetrahydrofuran-3-ones 76 and subsequent transformation.
Scheme 48
Scheme 48
Dipolar cycloaddition of cyclic α-diazo ketones with acetylenes.
Scheme 49
Scheme 49
The influence of the ring size of the α-diazo ketone on the outcome of dipolar cycloaddition.
Scheme 50
Scheme 50
Synthesis of bis(trifluoromethyl)pyrazoles 86.
Scheme 51
Scheme 51
Formation of a dimeric product in dipolar cycloaddition with benzyne.
Scheme 52
Scheme 52
Dipolar cycloaddition with benzyne of more rigid α-diazo ketones.
Scheme 53
Scheme 53
2-Diazo-1-indanone in Rh(II)-catalyzed cyclopropanation reactions.
Scheme 54
Scheme 54
Diastereoselectivity aspects of the 2-diazo-1-indanone behavior in Rh(II)-catalyzed cyclopropanation reactions.
Scheme 55
Scheme 55
3-Diazochroman-4-ones 91 in cyclopropenation reactions and further transformations.
Scheme 56
Scheme 56
Oxidative Pd-catalyzed cross-coupling of α-diazo ketones with arylboronic acids.
Scheme 57
Scheme 57
Oxidative coupling of α-diazo ketones with vinyl boronic acids.
Scheme 58
Scheme 58
α-Arylation with triphenyl boroxine.
Scheme 59
Scheme 59
Transformation of 6-diazocyclohex-2-enones 97 into arylphenols 99.
Scheme 60
Scheme 60
Using o-iodobenzoic acid methyl ester as the arylating agent.
Scheme 61
Scheme 61
Synthesis of axially chiral biphenyls.
Scheme 62
Scheme 62
Dibenzofuran synthesis via arylation/aromatization cascade followed by intramolecular Ullmann reaction.
Scheme 63
Scheme 63
Synthesis of biphenols.
Scheme 64
Scheme 64
Plausible mechanism for the Rh(III)-catalyzed formation of biphenols.
Scheme 65
Scheme 65
Synthesis of o-anilino-substituted phenols from 6-diazocyclohex-2-enones.
Scheme 66
Scheme 66
Alkaloid synthesis form o-anilino phenols.
Scheme 67
Scheme 67
Pd(II)-catalyzed synthesis of o-amino phenols from 6-diazocyclohex-2-enone.
Scheme 68
Scheme 68
Structures of two 18F PET tracers.
Scheme 69
Scheme 69
Synthesis of monofluorophenols 105 from 6-diazocyclohex-2-enones.
Scheme 70
Scheme 70
Synthesis of 2-fluoroestradiol from O-methyl estradiol.
Scheme 71
Scheme 71
Synthesis of monofluorophenols via bromofluorination.
Scheme 72
Scheme 72
The first synthesis of α-diazo-γ-butyrolactone.
Scheme 73
Scheme 73
Detrifluoroacetylative diazo transfer as the method for the preparation of α-diazo lactones.
Scheme 74
Scheme 74
Deacetylative diazo transfer using the SAFE diazo transfer protocol in an aqueous medium.
Scheme 75
Scheme 75
Oxidation of a hydrazone.
Scheme 76
Scheme 76
Azide reduction with NHS-containing phosphine.
Scheme 77
Scheme 77
Büchner–Curtius–Schlotterbeck reaction of α-diazo-γ-butyrolactones.
Scheme 78
Scheme 78
Cu(II) triflate catalyzed decomposition and rearrangement of tricyclic α-diazo-β-hydroxyvalerolactone 108.
Scheme 79
Scheme 79
Fragmentation of α-diazo-β-hydroxy-γ-silyloxylactones into macrocyclic products.
Scheme 80
Scheme 80
Formal insertion of α-diazo lactone-derived Rh(II) carbenes into various X-H bonds.
Scheme 81
Scheme 81
Comparison of α-diazo esters and α-diazo lactones in molecular orbital orientation.
Scheme 82
Scheme 82
Cytochrome-catalyzed S-H insertion reaction of α-diazo-γ-butyrolactones.
Scheme 83
Scheme 83
Cytochrome-catalyzed B-H insertion reaction of five- and six-membered α-diazo lactones.
Scheme 84
Scheme 84
Cascade Rh(II)-catalyzed S-H insertion—recyclization.
Scheme 85
Scheme 85
Spirocycle synthesis via X-H insertion into the molecule bearing an electrophilic moiety.
Scheme 86
Scheme 86
Ylide trapping by alkyne and alkyl bromide.
Scheme 87
Scheme 87
Cyclopropanation and cyclopropenation reactions of α-diazo lactones 113–114.
Scheme 88
Scheme 88
Rh(II)-catalyzed cyclopropenation of trimethylsilyl acetylene en route to (−)-quebrachamine (117).
Scheme 89
Scheme 89
Cytochrome-catalyzed cyclopropanation of styrenes.
Scheme 90
Scheme 90
C-H insertion reactions of α-diazo-γ-butyrolactones.
Scheme 91
Scheme 91
Intramolecular C-H insertion in the synthesis of naturally occurring furofuranones.
Scheme 92
Scheme 92
Bicyclic thiofuranone synthesis.
Scheme 93
Scheme 93
Oxidative cross-coupling with trans-vinyl boronic acids.
Scheme 94
Scheme 94
Example of preparation of α-diazo lactams via the nitrozation of an α-amino lactam.
Scheme 95
Scheme 95
N-Alkylation of unsubstituted six-membered α-diazo lactam 125.
Scheme 96
Scheme 96
Synthesis of α-diazo-γ-butyrolactams 127 via diazo transfer onto ethoxalylated derivatives 128.
Scheme 97
Scheme 97
AgOTf catalyzed decomposition of α-diazo-γ-butyrolactams 127.
Scheme 98
Scheme 98
‘Dimerization’ of N-alkyl or N-(o-aryl) α-diazo-γ-butyrolactams.
Scheme 99
Scheme 99
Diazo transfer onto N-Boc α-diazo-γ-butyrolactams 131 via α-dimethylaminomethylenation using the Broderick’s reagent (132).
Scheme 100
Scheme 100
Reduction of an azido lactam with an NHS-containing phosphine.
Scheme 101
Scheme 101
Reactions of α-diazo lactams with alkynes and α,β-unsaturated carbonyl compounds.
Scheme 102
Scheme 102
Rh(II)-catalyzed insertion of 3-diazopiperidine-2-one into the O-H bond of alcohols.
Scheme 103
Scheme 103
S-H insertion reaction of α-diazo-γ-butyrolactams under Rh(II) catalysis.
Scheme 104
Scheme 104
Rh(II)-catalyzed N-H insertion reactions of α-diazo-δ-valerolactams.
Scheme 105
Scheme 105
Evolution of 3-diazopiperidin-2-one via mild chloroselenylation.
Scheme 106
Scheme 106
Olefination of α-diazo-δ-valerolactams with aldehydes.
Scheme 107
Scheme 107
Rh(II)-catalyzed C-H insertion reaction of pyrroles and indoles.
Scheme 108
Scheme 108
Selective cyclopropanation of allyl vinyl ether.
Scheme 109
Scheme 109
The Büchner–Curtius–Schlotterbeck reaction of α-diazo-γ-butyrolactams with cyclic ketones.
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References

    1. Ye T., McKervey M.A. Organic Synthesis with a-Diazo Carbonyl Compounds. Chem. Rev. 1994;94:1091–1160. doi: 10.1021/cr00028a010. - DOI
    1. Ford A., Miel H., Ring A., Slattery C.N., Maguire A.R., McKervey M.A. Modern Organic Synthesis with α-Diazocarbonyl Compounds. Chem. Rev. 2015;115:9981–10080. doi: 10.1021/acs.chemrev.5b00121. - DOI - PubMed
    1. Burke S.D., Grieco P.A. Organic Reactions. John Wiley & Sons, Inc.; Hoboken, NJ, USA: 1979. Intramolecular Reactions of Diazocarbonyl Compounds; pp. 361–475.
    1. Liu L., Zhang J. Gold-Catalyzed Transformations of α-Diazocarbonyl Compounds: Selectivity and Diversity. Chem. Soc. Rev. 2016;45:506–516. doi: 10.1039/C5CS00821B. - DOI - PubMed
    1. DeAngelis A., Dmitrenko O., Fox J.M. Rh-Catalyzed Intermolecular Reactions of Cyclic α-Diazocarbonyl Compounds with Selectivity over Tertiary C–H Bond Migration. J. Am. Chem. Soc. 2012;134:11035–11043. doi: 10.1021/ja3046712. - DOI - PMC - PubMed

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