Cyanophosphate: An efficient intermediate for conversion of carbonyl compounds to nitriles

Yoneda, R.; Harusawa, Shinya; Kurihara, Takushi

doi:10.1016/s0040-4039(01)80482-2

Cited by 37 publications

(14 citation statements)

References 12 publications

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“…Work-up as described for the hydrolysis of compound 11, followed by chromatography with hexane-ethyl acetate (8 : 2) as eluent, gave acids 14 (6.4 mg, 60%) and 9 (3.8 mg, 40%). Data for the acid 14,dH(40O MHz) 6.24 (1 H, dd, J2.9 and 1.0,15-H),6.19 (1 H,d, J2.9,17-H),4.93(1 H,dd, J2.9and 2.9,7-H), 2.77 (1 H, ddd, J 12.5,6.4 and 3.7,13-H), 2.73 (1 H, br d, J3.7, 14-H), 2.05 (3 H,s,OAc),1.29 (1 H,dd,J 12.4 and 2.2, 5-H) and 0.80,0.78 and 0.77 (9 H, 3 s, 4a-, 4P-+ 1OP-Me); m/z (EI)318(0.7%), 301 (2), 300 (8),285 (7),231 (5), 176 (7), 131 (12), 117 (25), 55 (26) and 43 (100); dC see Table 1.…”

Section: Methodsmentioning

confidence: 99%

Spongian pentacyclic diterpenes. Stereoselective synthesis of aplyroseol-1, aplyroseol-2 and deacetylaplyroseol-2

Abad¹,

Arnó²,

Marín³

et al. 1993

J. Chem. Soc., Perkin Trans. 1

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Section: Methodsmentioning

confidence: 99%

Spongian pentacyclic diterpenes. Stereoselective synthesis of aplyroseol-1, aplyroseol-2 and deacetylaplyroseol-2

Abad¹,

Arnó²,

Marín³

et al. 1993

J. Chem. Soc., Perkin Trans. 1

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“…18,19) Thus, these reductive dephosphorylation reactions have potential for application in the preparation of CPs derived from enones and aromatic ketones. 1) We further developed the reductive cyanation of CPs using SmI 2 , which is a moderate reducing agent 20,21) (Table 4). This method also yielded nitriles chemoselectively from various carbonyl compounds possessing multiple and sensitive functionalities via CPs (entries 1-6, Table 4).…”

Section: Reductive Cyanation Of Ketones and Aldehydesmentioning

confidence: 99%

“…For example, cyanation of epoxy aldehyde 25 was conducted by a combination of cyanophosphorylation and SmI 2 reduction followed by recyclization of the oxirane ring-opened product with triethylamine, to give the epoxy nitrile 26 in 54% yield (entry 7). 20) This reaction was successfully applied to α,β-unsaturated carbonyl compounds under neutral conditions to obtain the desired nitriles. Cholest-4-en-3-one (27) and α-ionone (29) gave the corresponding nitriles 28 and 30 (entries 9 and 10, Table 4), whereas under general tosylmethyl isocyanide (TosMIC) 22) conditions in the presence of t-BuOK in DMF, nitriles 28 and 30 were detected only by TLC in trace amounts.…”

Section: Reductive Cyanation Of Ketones and Aldehydesmentioning

confidence: 99%

“…Cholest-4-en-3-one (27) and α-ionone (29) gave the corresponding nitriles 28 and 30 (entries 9 and 10, Table 4), whereas under general tosylmethyl isocyanide (TosMIC) 22) conditions in the presence of t-BuOK in DMF, nitriles 28 and 30 were detected only by TLC in trace amounts. 20) The CPs-SmI 2 method was employed in a variety of organic syntheses, 1) for instance, in the synthesis of the natural spongian pentacyclic diterpene, aplyroseol-1 and its related compounds; in the synthesis of hydroxyethene isosteres of human immunodeficiency virus (HIV) protease-catalyzed phenylalanine (Phe)-proline (Pro) hydrolysis transition state; in the transformation of aldol product from Boc-L-phenylalaninal into lactone; in the synthesis of sweroside aglycon; and in the preparation of nitriles from chiral ketone in the total synthesis of (±)-aphidicolin.…”

Section: Reductive Cyanation Of Ketones and Aldehydesmentioning

confidence: 99%

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Development of New Synthetic Reactions Using Hetero-Heavy Atoms and Their Application to Synthesis of Biofunctional Molecules

Harusawa

2020

CHEMICAL & PHARMACEUTICAL BULLETIN

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Novel reactions using hetero-heavy atoms (P, S, Si, Se, and Sn) were developed and applied to the synthesis of biofunctional molecules and some medicine-candidates, in which the following items are covered. 1) Development of introduction of C 1-unit using cyanophosphates (CPs). 2) Carbene-generation under neutral condition from CPs and its application to organic synthesis. 3) [3,3]Sigmatropic rearrangement-ring expansion reactions of medium-sized cyclic thionocarbonates containing a sulfur atom and their application to natural product synthesis. 4) Stereoselective synthesis of novel β-imidazole C-nucleosides via diazafulvene intermediates and their application to investigating ribozyme reaction mechanism. 5) Developments of novel histamine H 3-and H 4-receptor ligands using new synthetic methods involving Se or Sn atoms.

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“…The reduction of cyanophosphates 46, readily prepared from ketones or aldehydes with diethyl phosphorocyanidate and lithium cyanide, led to nitriles in excellent yields [132] (Scheme 54). This reductive cyanation process has also Scheme 54 been applied to conjugated enones or enals, giving `,a-unsaturated nitriles without products from the migration of the double bond.…”

Section: Cleavage Of Carbon-heteroatom Bondsmentioning

confidence: 99%

Lanthanides: Chemistry and Use in Organic Synthesis

Kobayashi¹

1999

Topics in Organometallic Chemistry

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they are for gaseous ions. These transitions are "LaPorte-forbidden" and result in weak intensities which are responsible for the pale color of the trivalent species. General principles of d-transiton metal ligand bonding such as m-donor//acceptor interaction, the "18-electron rule", and the formation of classic carbene, carbyne, or carbon monoxide complexes are not observed in lanthanide chemistry, neither do they form Ln=O or Ln>N multiple bonds. However, the lack of orbital restrictions, e.g. the necessity to maximize orbital overlap as in d-transition metal chemistry, allows "orbitally forbidden" reactions. Because of very small crystal-field splitting and very large spin-orbit coupling (high Z) the energy states of the 4f n electronic configurations are usually approximated by the Russel-Saunders coupling scheme [18]. The peculiar electronic properties of the f-elements have proved attractive for numerous intriguing opto-and magneto-chemical applications ("probes in life") [15].The inert gas-core electronic configuration also implies a conform chemical behavior of all of the Ln(III) derivatives including Sc(III), Y(III) and La(III). The contracted nature of the 4f-orbitals and concomitant poor overlap with the ligand orbitals contribute to the predominantly ionic character of organolanthanide complexes. The existing electrostatic metal ligand interactions are reflected in molecular structures of irregular geometry and varying coordination numbers. According to the HSAB terminology of Pearson [19], lanthanide cations are considered as hard acids being located between Sr(II) and Ti(IV). As a consequence, "hard ligands" such as alkoxides and amides, and also cyclopentadienyl ligands show almost constant effective ligand anion radii (alkoxide: 2.21±0.03 Å; amide: 1.46±0.02; cyclopentadienyl: 1.61±0.03) [20] and therefore fit the evaluation criteria of ionic compounds according to Eigenbroth and Raymond [21]. The ionic bonding contributions in combination with the high Lewis acidity cause the strong oxophilicity of the lanthanide cations which can be expressed in terms of the dissociation energy of LnO [12]. The interaction of the oxophilic metal center with substrate molecules is often an important factor in governing chemo-, regio-and stereoselectivities in organolanthanide-catalyzed transformations [22]. Complexation of the "softer" phosphorus and sulfur counterions is applied to detect extended covalency in these molecular systems [23,24].Scheme 1 further indicates the tendency of the Ln(III) cations to form the more unusual oxidation states in solution [25]. Hitherto, organometallic compounds of Ce(IV), Eu(II), Yb(II) and Sm(II) have been described in detail [4]. More sophisticated synthetic approaches involving metal vapor co-condensation give access to lower oxidation states of other lanthanide elements [26]. Charge dependent properties such as cation radii and Lewis acidity significantly differ from those of the trivalent species. Ln(II) and Ce(IV) ions show very intense and ligand-dependent colors attrib...

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Cyanophosphate: An efficient intermediate for conversion of carbonyl compounds to nitriles

Cited by 37 publications

References 12 publications

Spongian pentacyclic diterpenes. Stereoselective synthesis of aplyroseol-1, aplyroseol-2 and deacetylaplyroseol-2

Spongian pentacyclic diterpenes. Stereoselective synthesis of aplyroseol-1, aplyroseol-2 and deacetylaplyroseol-2

Development of New Synthetic Reactions Using Hetero-Heavy Atoms and Their Application to Synthesis of Biofunctional Molecules

Lanthanides: Chemistry and Use in Organic Synthesis

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