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SPOTLIGHT

SYNLETT

Spotlight 294
This feature focuses on a reagent chosen by a postgraduate, highlighting the uses and preparation of the reagent in current research

Bestmann–Ohira Reagent: A Versatile Reagent in Organic Synthesis
Compiled by Umesh Daga Patil
Umesh D. Patil was born in Pimpri (Mondhale), Jalgaon, India, in 1984. He pursued his B.Sc. in chemistry (2005) from Kisan Mahavidyalaya Parola, affiliated to North Maharashtra University (NMU), Jalgaon, India, and his M.Sc. in Organic Chemistry (2007) at the Department of Organic Chemistry, NMU. At present he is working towards his Ph.D. at the same department under the guidance of Dr. Sidhanath V. Bhosale. His research interests include the synthesis of biologically active heterocyclic compounds using ring transformations. Department of Organic Chemistry, North Maharashtra University, Umavinagar, Jalgaon 425001, India E-mail: umesh123patil@gmail.com Dedicated to Professor S. L. Patil

Introduction
Bestmann–Ohira reagent [(1-diazo-2-oxopropyl)phosphonate] can be prepared by the reaction of dimethyl-2oxopropylphosphonate, TosN31a or p-acetamidobenzenesulfonyl azide,1b NaH, t-BuOK or Et3N in benzene and THF. An alternative is the preparation using polymer-supported sulfonyl azide and t-BuOK in methylenchloride.1c The Bestmann–Ohiro reagent is widely used in the con-

version of primary alcohols, aldehydes, ketones, and amides into alkynes. Recently, it was employed in the synthesis of pyrazoles as well as 1,3-oxazoles.
O eMO eMO P H eMO R R O
1R

Scheme 1

Abstracts
HOeM ,3OC2K

SYNLETT 2009, No. 17, pp 2880–2881xx. 209 Advanced online publication: 02.10.2009 DOI: 10.1055/s-0029-1218101; Art ID: V29809ST © Georg Thieme Verlag Stuttgart · New York

eM2OC = X 2ON = X

X

tnegaer arihO–nnamtseB .2

2OnM

.1

HO

X

(C) E. Quesada et al. described the direct conversion of activated primary alcohols into terminal alkynes through a sequential one-pot, two-step process involving oxidation with manganese dioxide and then treatment with the Bestmann–Ohira reagent. This transformation proceeds efficiently (59–99% yield) under mild reaction conditions with a range of benzylic, heterocyclic, and propargylic alcohols.4

tnegaer arihO–nnamtseB .2

C° 87– ,2lC2HC ,H-LABID .1

4R

O

O

1

R

ro

3

R

2R

N

O

1R

(B) Hamilton D. Dickson and co-workers reported that esters and amides undergo reduction to the corresponding aldehydes using DIBAL-H followed by in situ conversion into terminal alkynes utilizing the Bestmann–Ohira reagent in good to excellent yields.3 Additionally, chiral nonracemic substrates undergo this transformation with complete preservation of stereochemical integrity.3

H

R

HOeM ,3OC2K

h 81–4 ,.t.r

.t.r

tnegaer arihO–nnamtseB

tnegaer arihO–nnamtseB

OHC

OHCR

R

(A) The use of the Bestmann–Ohira reagent is an alternative to the Fritsch–Buttenberg–Wiechell-type rearrangement and the Corey– Fuchs procedure that allows the addition of the reagent to an aldehyde under mild reaction conditions, thus avoiding the use of a strong base under low-temperature conditions. The reaction works with alkyl and aryl as well as hindered aldehydes. In case of a,bunsaturated aldehydes the main products were isolated as homopropargylic methyl ethers. The reaction can be easily performed under one-pot conditions.2

FHT ni ediza lynoflusenezneb

-odimateca-p .2 eMO eMhP ,HaN .1 eMO P

tnegaer arihO–nnamtseB

O
2N

O eMO FHT ,6H6C eMO P N3tE ro HaN ,3NsoT O O

9.3oxazoles conveniently by reaction of Bestmann–Ohira reagent and aromatic nitriles in the presence of a catalytic amount of rhodium(II) acetate. Gong et. U. (11) Ohira. Int. (8) Barrett.. Smith. Commun.rA = R tEO P OtE O R . Commun.. 155.t. A.. C.8 The use of polymer-supported Ohiro reagent led to high product yield. 45. G. 2004. Mobin. Hinkle. Ed. (2) Müller. (9) Bartnik. J... 6473. 44. Flynn.. D’haenens. The alkynes are obtained in modest to excellent yields. Hanson. Org. Synth. Sherrill.. Angew. Lett. Witt.t. M. 2005. D. B. No. P. 34. (4) Quesada. Synlett 1996. 5597. 2004. L.. S. 835. 45.10 tEO tEO O P N N N hP R d 3 .1 tnegaer arihO .SPOTLIGHT 2881 References (1) (a) Callant. 2005. A. Synth. S. Chem. Wasiak.rA = R tEO tEO N P H N O X R (D) 1.7 N tEO tEO P O 2 R O 1R )%lom 1( 4)cAO(2hR C° 58 NC2R + tnegaer arihO–nnamtseB tEO tEO SPIT O P 2N R O 1R (E) D. S.3]triazol-4-yl)-phosphonic acid diethyl ester. H. Commun. S.. 47.tEOaN X tEO tEO 2ON tnegaer arihO–nnamtseB O P 2N O X 2eMN 2ON .2. Tetrahedron Lett. K. 2880–2881 © Thieme Stuttgart · New York eMO 3 R 1R 2R tnegaer arihO–nnamtseB HOeM .. 7301. H.. W.r HOeM H R N hP (H) The cycloaddition of diethyl 1-diazomethylphosphonate with benzylidine alkylamines afford (1-alkyl-5-phenyl-4.3OC2K 3 O R 1R (J) The Bestmann–Ohira reagent itself was used for the preparation of enol ethers or alkynes from carbonyl compounds in the presence of excess potassium carbonate and methanol. M. Synth. (6) Gong.. C. Synlett 2009. N. Lesniak. 1125. N. L. A. Fallis. Yuan.O = X H ro rateH .klA = R H 2 O (G) Barrett and co-workers prepared ROMPgel-supported ethyl 1diazo-2-oxopropylphosphonate and employed this reagent in the conversion of a variety of aldehydes into terminal alkynes. W.rB . 561. P. 61.r . Synthesis 2006. 1984. described the base-promoted reaction of dimethyl (diazomethyl)phosphonate with aldehydes and aryl ketones at low temperature. 2004.6 HN N R X HC .. R. 4039. C. al.0 HOtE ..tEOaN 2ON . Tetrahedron Lett. Tetrahedron Lett. Tetrahedron 2005. with conjugated nitroalkenes provided regioisomerically pure phosphonylpyrazoles in moderate to good yield. M.. 6. S. (7) Clay. 521. 3259... E. J.H = X . prepared a series of 4-phosphoryl-substituted 1. R.9 + 2)tEO(OPHC2N dleiy %19–36 H R HOeM ni sllews legPMOR ralop O 2N HOeM . 4266.. 1837.5 ..r . 19. Liepold. Chem. 1982. D. M. (3) Dickson. L. M.h 42–5. Org.. A. J. Love. 46. generated in situ from Bestmann-Ohira reagent. 14.. Tedeschi. Lett. Zhang. G.2 HO O (F) Oxidation of epoxy alcohol by Dess– Martin periodinane gave an aldehyde which was subsequently treated with the Ohiro reagent to give an epoxy alkyne in 93% yield. J. M.rateH . R. Org.nim 01–5 HOtE . I. K. A. 2007. D. (b) Pietruszka. Hopkins.3OC2K O OtE P O PMOR rA .5-dihydro-1H[1. P. C.11 RC CrA KOuB-t ro iLuB-n ROCrA + 2)tEO(OPHC2N (I) Gilbert et al. R O SPIT enanidoirep nitraM–sseD ... L. (5) Muruganantham. D. These pyrazoles are formed in one pot via spontaneous elimination of the nitro group. (c) Harned. 17. 1989. Vandewalle. (10) Gilbert. Bestmann. Namboothiri.3-Dipolar cycloaddition of the anion of diethyl 1-diazomethylphosphonate. B. T. R. Weerasooriya. 2004.t. J. 12093. Taylor.

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