Arylmethyl phenyl sulfones, a new carbon nucleophile for Mitsunobu-type alkylation

Tsunoda, Tetsuto; Uemoto, Kaori; Ohtani, Tomoko; Kaku, Hiroto; Itô, Shô

doi:10.1016/s0040-4039(99)01510-5

Cited by 25 publications

(13 citation statements)

References 13 publications

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“…The use of new reagents for Mitsunobu reactions, as developed by Tsunoda et al, [5] did not improve the yield. Oxidation of 9 to (R)-nocardione B was first attempted with Fremy's salt.…”

Section: Introductionmentioning

confidence: 97%

Synthesis and Absolute Configuration of Nocardione A and B, Furano-o-naphthoquinone-Type Metabolites of Nocardia sp. with Antifungal, Cytotoxic, and Enzyme Inhibitory Activities

Tanada

Mori

2001

Eur. J. Org. Chem.

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“…The use of new reagents for Mitsunobu reactions, as developed by Tsunoda et al, [5] did not improve the yield. Oxidation of 9 to (R)-nocardione B was first attempted with Fremy's salt.…”

Section: Introductionmentioning

confidence: 97%

Synthesis and Absolute Configuration of Nocardione A and B, Furano-o-naphthoquinone-Type Metabolites of Nocardia sp. with Antifungal, Cytotoxic, and Enzyme Inhibitory Activities

Tanada

Mori

2001

Eur. J. Org. Chem.

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“…4) with pK a of 11-23, such as N-methyltosylamide (3, pK a 11.7), 5,6) (cyanomethyl)phenylsulfone (4, pK a 12.0 in DMSO 7) ), 5,6) (methylthiomethyl)tolylsulfone (5, pK a 23.4 in DMSO 8) ), 5,6) benzyl phenyl sulfone (6a, pK a 23.4 in DMSO 9) ), 10) 3-[(phenylsulfonyl)methyl]pyridine (6b, pK a 16.7 in DMSO 9) ) 10) and geranyl phenyl sulfone (7, pK a 22.5 in DMSO 9) ).…”

mentioning

confidence: 99%

Preparation of (Cyanomethylene)trimethylphosphorane as a New Mitsunobu-Type Reagent.

Izumi

Kaku

Tsunoda

2003

CHEMICAL & PHARMACEUTICAL BULLETIN

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The Mitsunobu reaction is a very versatile method for the alkylation of various nucleophiles (HA) with alcohols (ROH) to give RA, utilizing the redox system of diethyl azodicarboxylate (DEAD)-triphenylphosphine (TPP) (Fig. 1). 1,2) Without any prerequisite activation of the alcohol, it is a unique alkylation reaction and widely applied to various phases of organic synthesis. However, the reaction has a serious limitation; the acidic hydrogen in HA has to have pK a lower than 11 for the reaction to proceed satisfactorily. If HA has a pK a higher than 11, the yield of RA is considerably lower, and with HA having a pK a higher than 13, the desired reaction does not occur. In order to overcome these drawbacks and expand the versatility of the original Mitsunobu reaction, stabilized trialkylphosphoranes such as (cyanomethylene)tributylphosphorane (CMBP) 3) and (cyano-methylene)trimethylphosphorane (CMMP) 4) have been developed to replace the DEAD-TPP system.These new reagents were designed based on the structural similarity between the ylide 2 and the betaine 1 generated as an important intermediate in the Mitsunobu reaction (Fig. 2). The ylide 2, which is another resonance form of trialkylphosphorane, was expected to behave similarly with 1 towards a mixture of ROH and HA to yield RA along with the by-products, trialkylphosphine oxide and acetonitrile (Fig. 3).In fact, the trialkylphosphoranes, especially CMMP, mediate the Mitsunobu-type reactions of various kind of nucleophiles (Fig. 4) with pK a of 11-23, such as N-methyltosylamide (3, pK a 11.7), 5,6) (cyanomethyl)phenylsulfone (4, pK a 12.0 in DMSO 7) ), 5,6) (methylthiomethyl)tolylsulfone (5, pK a 23.4 in DMSO 8) ), 5,6) benzyl phenyl sulfone (6a, pK a 23.4 in DMSO 9) ), 10) 3-[(phenylsulfonyl)methyl]pyridine (6b, pK a 16.7 in DMSO 9) ) 10) and geranyl phenyl sulfone (7, pK a 22.5 in DMSO 9) ).11)The useful attributes of the new Mitsunobu reaction are as follows. 1) These reactions with secondary alcohols proceed with the complete Walden inversion of the stereochemistry at the carbinyl carbon.2) The reaction of the DEAD-TPP redox system (the traditional Mitsunobu reaction) is not normally effective at higher temperature, whereas the reaction of CMBP and CMMP even at higher temperature can be carried out satisfactorily, because they are quite thermally stable although very sensitive to air and moisture. Furthermore, 3) in the traditional Mitsunobu reaction, one problem is the laborious purification of the product from dihydro-DEAD and triphenylphosphine oxide, whereas the use of the phosphoranes leads to an easy workup. Acetonitrile produced in place of dihydro-DEAD can be easily evaporated, and the removal of tributyl-or trimethylphosphine oxide can be attained by SiO 2 column chromatography because of its high polarity. As an alternative workup for the reaction with CMMP, aqueous treatment of the reaction mixture is also quite effective because of the good aqueous solubility of trimethylphosphine oxide.Thus, the very high reactivity observed for the bond for...

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“…High yields of the alkylation product with the classical oxidation-reduction system have been recorded for compounds with pK a < 15 [3]. Other oxidation-reduction systems -combinations of tributylphosphine and amides of azodicarboxylic acid such as azodicarbonyldipiperidine (ADDP) [12], tetramethylazodicarboxamide (TMAD) [13,14], dimethylhexa-hydrotetrazocinedione (DHTD) [13,14], phosphoranes (cyanomethylenetributylphosphorane, CMBP) [13,14], and cyanomethylenetrimethylphosphorane (CMMP) [13,14] − have been proposed in order to extend the Mitsunobu reaction to substrates with larger pK a values. .…”

Section: The General Characteristics and Certain Aspects Of The Mechamentioning

confidence: 99%

The Mitsunobu reaction in the chemistry of nitrogen-containing heterocyclic compounds. The formation of heterocyclic systems (review)

Голанцов

Карчава

Yurovskaya

2008

Chem Heterocycl Comp

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Methods for the design of nitrogen-containing heterocyclic systems involving the formation of C-N bonds under the conditions of the Mitsunobu reaction are discussed.The Mitsunobu reaction [1][2][3][4] is the reaction of compounds containing a mobile hydrogen atom HX with alcohols in the presence of a reagent system consisting of an azodicarboxylic ester and a phosphine PR 1 3 . This reaction results in the formation of an alkylation product RX accompanied by oxidation of the phosphine PR 1 3 to phosphine oxide R 1 3 P=O and reduction of the azodicarboxylic ester to the corresponding hydrazine.The reaction takes place under very mild conditions and usually at room temperature. If a chiral secondary alcohol ROH is used, the reaction is usually stereospecific and is accompanied by inversion of the configuration at the asymmetric carbon atom of the alcohol [1-3].From the moment of the first report [5] the Mitsunobu reaction became a powerful tool in synthetic organic chemistry and found widespread use in the synthesis of various heterocyclic compounds, optically active substances, steroids, alkaloids, carbohydrates, and nucleosides [1][2][3][4]6]. In particular, in a number of cases the Mitsunobu reaction has made it possible to synthesize new physiologically active compounds or to put forward new highly effective approaches to synthesis. Several reviews have been devoted to the Mitsunobu reaction [1-4, 6, 7]. Data on the use of the Mitsunobu reaction in the synthesis of alkaloids were reviewed in [6]. Various experimental techniques that make it possible to simplify the isolation of the products of the Mitsunobu reaction RX from the reaction mixture, including the use of reagents attached to a polymer support, were discussed in [7]. _______ * Dedicated to Afanasi Andreevich Akhrem on his 95th birthday. _________________________________________________________________________________________

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Arylmethyl phenyl sulfones, a new carbon nucleophile for Mitsunobu-type alkylation

Cited by 25 publications

References 13 publications

Synthesis and Absolute Configuration of Nocardione A and B, Furano-o-naphthoquinone-Type Metabolites of Nocardia sp. with Antifungal, Cytotoxic, and Enzyme Inhibitory Activities

Synthesis and Absolute Configuration of Nocardione A and B, Furano-o-naphthoquinone-Type Metabolites of Nocardia sp. with Antifungal, Cytotoxic, and Enzyme Inhibitory Activities

Preparation of (Cyanomethylene)trimethylphosphorane as a New Mitsunobu-Type Reagent.

The Mitsunobu reaction in the chemistry of nitrogen-containing heterocyclic compounds. The formation of heterocyclic systems (review)

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