REGISTRATION NO: 20CHMS55.

NAME: SUMAN MONDAL.

Subject code- CY-584.
M.Sc 4th semester.

LITERATURE SURVEY ON SWERN OXIDATION

INTRODUCTION : The Swern oxidation, named after Daniel Swern, is a chemical

reaction whereby a primary or secondary alcohol is oxidized to an aldehyde or ketone using oxalyl
chloride,dimethyl sulfoxide (DMSO) and an organic base, such as triethylamine. The oxidation was
discovered by Moffat, but a very popular modification using oxalyl chloride/triethylamine was
introduced by Swern, so the reaction is often referred to as a Swern oxidation. The reaction is known
for its mild character and wide tolerance of functional groups. Current continuous flow reactor (CFR)
development and optimization primarily involves the investigation of process parameters such as flow
and temperature to optimize a reaction. The advantages of CFRs for stable production – including
improved heat transfer, reproducible results, safety and cost considerations, and others –
generally result in comparable or improved
yield compared to batch chemistry.
ADVANTAGES:
 Atom efficiency (by-products):
Moderately atom efficient for an
oxidation.
 Cost, availability & sustainable
feedstocks: Reagents are cheap and
readily available, but the use of
oxalyl chloride has now been
largely phased out with other
DMSO activators.
 Sustainable implications: No large
issues with reagents. Sustainability issues are usually dominated by solvents, normally
chlorinated,used for the Swern oxidation.

LIMITATION : Two of the by-products, dimethyl sulfide and carbon monoxide, are very toxic

volatile compounds, so the reaction and the work-up needs to be performed in a fume hood.Dimethyl
sulfide is a volatile liquid (B.P. 37 °C) with an extremely unpleasant odour.

SOME RECENT EXAMPLES OF SWERN OXIDATION:

 CYCLOPROPENIUM-ACTIVATED DMSO FOR SWERN-TYPE OXIDATION:

ADVANTAGES:
Swern oxidation using
the volatile oxalyl
chloride as an
activator requires
reaction temperatures
below -60 °C. 3,3-
Dichloro-1,2-
diphenylcyclopropene
(DDC) can be used as
a new activator at −20
°C.
 This convenient
new protocol
offers mild and
fast reactions.
 Furthermore, the activator DDC is easy to handle, and diphenylcyclopropenone can
be recovered quantitively.

 NEW ODORLESS METHOD FOR THE COREY-KIM AND SWERN OXIDATIONS

UTILIZING DODECYL METHYL SULFIDE (DOD-S-ME):

ADVANTAGE:
 Dodecyl methyl sulfide is an odorless alternatives to dimethyl sulfide in
Swern and Corey-Kim Oxidations. 

 SWERN OXIDATION OF ALCOHOLS WITH ION-SUPPORTED METHYL

SULFOXIDE AND OXALYL CHLORIDE:
 ADVANTAGE:
 The oxidation of primary and secondary alcohols with ion-supported methyl
sulfoxide and oxalyl chloride in the presence of triethylamine in
dichloromethane efficiently gives carbonyl compunds in good yields with
high purity.
 Isolation of the product was achieved very easily by simple diethyl ether
extraction of the reaction mixture.
 Furthermore, ion-supported methyl sulfide was recovered in good yield and
re-oxidized.
PROCESS TO FLOW:
When converting the process to flow, the Yoshida group found that the Swern oxidation could be
done at room temperature with good yields and purity. Moreover, instead of having reaction times on
the order of minutes or hours, the whole process was completed in seconds. They attributed the
success of their process to the precise temperature control that can be obtained in flow systems, as
well as the ability to quickly transfer unstable intermediates to subsequent steps. Using only a series
of syringe pumps, stainless steel tubing, and commercial micromixers, they could prepare over 10
grams of material per hour. Being able to perform reactions on species with very short lifetimes is
another general advantage of performing reactions in flow.

ADVANTAGE OF FLOW:
• Eliminates need for cryogenic conditions and dropwise addition of reagents.
• Low risk of thermal runaway.
• ~10g/hour in a <2 mL microreactor.
• Reaction complete in seconds instead of minutes or hours.
The CFR system far outperformed the batch setup in being able to generate product at temperature
higher than - 20°C. The success of this approach can set a standard for future approaches of
converting a batch reaction into a continuous process.
 Using TFAA as a DMSO activator seems to
afford even higher temperatures.

REFERENCES:

 T. Guo, Y. Gao, Z. Li, J. Liu, K. Guo, Cyclopropenium-Activated DMSO for Swern-Type

Oxidation.Synlett, 2019, 30, 329-332.
 D. Tsuchiya, K. Moriyama, H. Togo, Synlett, 2011, 2701-2704.
 S.-I. Ohsugia, K. Nishidea, K. Oonob, K. Okuyamab, M. Fudesakaa, S. Kodamaa, M.
Node, New odorless method for the Corey-Kim and Swern oxidations utilizing dodecyl
methyl sulfide (Dod-S-Me)Tetrahedron, 2003, 59, 8393-8398.
 https://www.allfordrugs.com/2015/07/20/flow-chemistry-can-make-processes-greener-swern-
oxidation/