Cyclic Sulfites and Cyclic Sulfates in Organic Synthesis

doi:10.1016/S0040-4020(00)00494-4

Tetrahedron

Volume 56, Issue 37, 8 September 2000, Pages 7051-7091

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Introduction

Although cyclic sulfate esters have been known since 1932,¹ the lack of an efficient method for preparing cyclic sulfates limited their applications. The oxidation of cyclic sulfites with sodium periodate catalyzed by ruthenium tetroxide² represents an important development that has broadened the use of cyclic sulfate intermediates in synthesis. The advent of the catalytic asymmetric dihydroxylation reaction provides a route to chiral 1,2-diols from a wide spectrum of olefins,³ which can be further elaborated to cyclic sulfates.⁴ The significant role of cyclic sulfates in organic synthesis originates from several properties. First, they have high reactivity toward various nucleophiles and are more reactive than epoxides. Second, they can activate nucleophilic attack at one position while serving as a protecting group at a second position; under more vigorous conditions they can serve as an activator for two sequential reactions. Third, the reactions of five-membered cyclic sulfates with nucleophiles provide two contiguous stereocenters; moreover, a remote stereocenter can be controlled by cyclic sulfates of 1,3- and 1,4-diols. Finally, since the intermediate of nucleophilic substitution is generally the salt form of a monosulfate ester, separation of the product from the nonsalt byproduct is typically a facile process.

Section snippets

Nomenclature

The IUPAC nomenclature system for heterocyclic systems⁵ is used in the naming of cyclic sulfites and cyclic sulfates. The appropriate stem is selected according to the size of the ring and the degree of unsaturation. Since the ring contains two oxygen atoms and one sulfur atom, the prefix dioxathi is used; the suffixes 2-oxide and 2,2-dioxide are used to distinguish between cyclic sulfites and cyclic sulfates, respectively. The numbering of the ring begins with one oxygen atom and proceeds

Reactivity

The carbon atoms in the cyclic sulfate moiety are highly reactive toward nucleophilic reagents. The enhanced reactivity relative to an acyclic sulfate may originate from two sources: (i) ring strain and (ii) partial double bond character between the ring oxygen atoms and the sulfur atom.^6a Ring strain may arise from the difference in the internal O–S–O bond angle in the cyclic sulfate vs. that in the pentacoordinate intermediate. The internal O–S–O bond angle, as determined by X-ray

Via non-chiral induction at the sulfur atom

Cyclic sulfites have been prepared by the reaction of epoxides with sulfur dioxide and by the reaction of 1,2- or 1,3-diols with Et₂NSF₃ (DAST) (, ).¹⁰ The most efficient synthesis of cyclic sulfites is the reaction of thionyl chloride with a diol¹¹ or transesterification of a dialkyl sulfite with a diol (Eq. (4)).¹² The neat reaction of ethylene glycol with thionyl chloride furnished ethylene sulfite in moderate yields; however, the yield was improved by the addition of methylene chloride.⁹ It

Regioselectivity of nucleophilic substitution

We consider here the regioselective nucleophilic ring opening of 3-O-benzyl 1,2-cyclic sulfite (34) and 1-(4′-methoxyphenyl)-glycerol 2,3-cyclic sulfate (37). These substrates have been chosen because one of the carbon atoms of the cyclic ester groups is a primary and the other is a secondary carbon. In addition to nucleophilic substitutions by external nucleophiles, intramolecular opening and Payne rearrangement of cyclic sulfates are also emphasized in view of their different

Resolution of chiral diols

Enantiomerically pure diols, especially with C₂ symmetry, are used as chiral auxiliaries or as precursors of diethers, bis(phospholanes), and diamines.106., 107. Lipases has been used for efficient separation of racemic diols. However, lipases cannot efficiently resolve racemic diols if the corresponding meso diols are also present, which is often the case in commercially available diols.¹⁰⁸ Cyclic sulfite chemistry has been used to remove meso diols from racemic diols, since the reaction of a

Acknowledgements

The work cited in this review from the author's laboratory was supported in part by National Institutes of Health Grant HL 16660.

Hoe-Sup Byun was born in 1947 in Seoul, Korea. He obtained the BS and MS degrees from Korea University, Seoul, South Korea, in 1974 and 1977, respectively. After he moved to New York in 1979, he investigated photolytic reactions of chloropropane and earned a PhD degree from The City University of New York under the direction of Professor M. H. Joseph Wijnen in 1984. He began research in lipid synthetic chemistry in Professor Bittman's laboratory in 1985. His main research interests are in the

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Linli He was born in 1964 in Zhejiang, People's Republic of China. He obtained a BS degree from Zhejiang University in Hangzhou, China in 1988. In 1994, he came to New York, where he obtained an MA degree in 1997 and a PhD degree in 2000 from The City University of New York. His dissertation research involved the asymmetric synthesis of analogues of glycerolipids and sphingolipids and the development of new methodologies for organic synthesis under the direction of Professor Robert Bittman.

Robert Bittman was born in New York City in 1942. He received a BS degree from Queens College of The City University of New York in 1962 and a PhD degree from the University of California at Berkeley in 1965 under the direction of Professor Andrew Streitwieser, Jr. After NSF postdoctoral work at the Max Planck Institute for Physical Biochemistry in Göttingen, Germany with Dr Manfred Eigen on the study of fast reactions of allosteric enzymes in solution, he returned to New York in 1966 to join the Department of Chemistry at Queens College of The City University of New York, where he has remained. Since 1988, his rank is University Distinguished Professor. His main research interests include the study of phospholipid–cholesterol interactions and the organization of sphingolipids in membranes by biophysical techniques, the synthesis and analysis of the mechanism of action of antitumor lipids, and the development of efficient strategies for the chemical synthesis of bioactive lipids, glycerolipids, and sphingolipids.

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Tetrahedron Report Number 538Cyclic Sulfites and Cyclic Sulfates in Organic Synthesis

Introduction

Section snippets

Nomenclature

Reactivity

Via non-chiral induction at the sulfur atom

Regioselectivity of nucleophilic substitution

Resolution of chiral diols

Acknowledgements

First page preview

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Tetrahedron Report Number 538
Cyclic Sulfites and Cyclic Sulfates in Organic Synthesis