Wasserman reaction

Cardiolipin or diphosphatidyl glycerol is one of the most ancient membrane phospholipids from phylogenic aspects. It is surprising for such a complex molecule as cardiolipin to have evolved as one of the major membrane lipids in prokaryotics, when steroids such as cholesterol and phytosterols did not. In eukaryotic cells, cardiolipin is exclusively localized within the mitochondria where it is particularly emiched in the outer leaflet of the inner membrane. Even though a molecular structure of cardiolipin has been conserved in entire organisms, its biological significance has escaped attention except in the case of anti-cardiolipin auto-antibodies which are clinically associated with the Wasserman reaction. 

Scott et al. (3) and Wasserman et al. (4) were the first to realize that this ring-opening polymerization, which had been known for several years, might be a special case of the metathesis reaction. 

L. W. Butz and A. W. Rytina, Org. React., 5, 136 (1949) M. C. Kloetzel, Org. React., 4, 1 (1948) A. Wasserman, Diels-Alder Reactions, Elsevier, New York (1965) F. Fringuelli and A. Tatacchi, Diels-Alder Reactions Selected Practical Methods, Wiley, New York, 2001. 

Wasserman (6) has reported the following data for this reaction. 

Wasserman (Diels-Alder Reactions, pp. 42, 50, and 52, Elsevier, London, 1965) has reported the following values of the reaction rate expression and heat of reaction for reaction conditions similar to those to be used in the proposed design analysis. This expression is valid over the range from 8 to 50 °C. 

A Mitsunobu process simultaneously coupled the enyne acid fragment 4 to /J-lactam 10 and inverted the CIO stereochemistry to the required (S)-configured ester 11 in 93% yield. A deprotection provided alcohol 12, the key /J-lactam-based macrolactonization substrate, which, under conditions similar to those reported by Palomo for intermolecular alcoholysis of /J-lactams (Ojima et al, 1992, 1993 Palomo et al, 1995), provided the desired core macrocycle 13 of PatA 13 (Hesse, 1991 Manhas et al, 1988 Wasserman, 1987). Subsequent Lindlar hydrogenation gave the required E, Z-dienoate. A Stille reaction and final deprotection cleanly provided (-)-PatA that was identical in all respects to the natural product (Romo etal, 1998 Rzasaef al, 1998). This first total synthesis confirmed the relative and absolute configuration of the natural product and paved the way for synthesis of derivatives for probing the mode of action of this natural product. 

E. Block, Reactions of organosulfur compounds, Vol 37 in Organic Chemistry, A.T. Blomquist and H.H. Wasserman (eds), Academic Press, New York, 1978. 

Searching for other oscillatory autoxidation reactions led Druliner and Wasserman to use cyclohexanone as a substrate instead of benzalde-hyde (168). Unlike the simple stoichiometry found for the benzaldehyde reaction, the ketone gives at least six or more products, and the relative amounts of these vary substantially with the experimental conditions (Scheme 7). 

Wasserman, A. Diels-alder reactions. New York Elsevier 1965 Onishchenko, A. S. Diene synthesis. Israel, Jerusalem S. Monson Binding 1964 Sauer, J., Wiest, H., Mielert, A. Z. Naturforsch. 17B, 203 (1962)... 

Wasserman ef f.62>93> have shown that syn-[2.2](l,4)naphthalenophane (34B) is converted into the anti form in 70% yield when irradiated with light of wavelength 3500 A in benzene for 10 days this reaction also proceeds thermally at 250 °C. Photolysis of the pure anti isomer... 

Wasserman et al.9T> irradiated a methanolic solution of 41 a in the presence of oxygen and methylene blue for 18 h at 25 °C. After hydrogenation of the reaction mixture over palladium on charcoal for 24 h they were able to isolate three products 120 (26%), 121 (11%), and 5% of a substance which was assigned structure 122 on the basis of spectroscopic and X-ray crystallographic data. The mechanism of formation of this polycycle probably involves an epoxide of type 123... 

Wasserman and Keehn ") have also carried out the photosensitized auto-oxidation of anti-[2.2](l,4)naphthalenophane (34A). Irradiation of anti-34 in methanol and simultaneous reaction with singlet oxygen affords the oxidation product 127 in 20% yield. The primary step in the reaction is assumed to be formation of a peroxide (128) whose geometry permits an intra-annular Diels—Alder reaction as second step methanol-ysis then leads to 127 which was isolated. 

Krusic PJ, Wasserman E, Keizer PN, Morton JR, Preston KF (1991) Radical reactions of Cm. Science 254 1183-1185. 

An interesting process of C-C bond formation is represented by the autooxidation of Mercurialis perennis L. plant alkaloid hermidin. The reaction proceeds through the formation of a transient blue anion-radical, which dimerizes with the transfer of the reaction center to give, eventually, chryso-hermidin as a dimeric hexaketone (Wasserman et al. 1993 Scheme 7.59). 

Wasserman, Diels-Alder Reactions, Elsevier, New York, 1965 R. Huisgen, R. Grashey, and J. Sauer, in... 

The Reactions of Diazoacetic Esters with Alkenes, Alkynes, Heterocyclic and Aromatic Compounds V. Dave and E. W. Warnhoff, Org. React., 1970,18, 217-402. Reactions of Singlet Oxygen with Heterocyclic Systems H. H. Wasserman and B. H. Lipshutz, Org. Chem., 1970, 40, 429-509. 

The stereochemistry of the Darzene condensation has received considerable attention in the literature. Early papers devoted to this aepeot of the reaction were those of Berson,1 Wasserman and oo-workere,1807-1808 and Stevens.,Ma From the work of these authors... 

A. Wasserman, Diels-Alder Reactions, Elsevier, New York, 1965. 

Wasserman et al. [286] reported a closely related reaction of an oxazole as shown in Scheme 63. The major product was formed via [4 + 2] cycloaddition of singlet oxygen, followed by rearrangement to 5-cyanopentanoic benzoic anhydride 161 and methanolysis to the cyano ester 162. In the case of the oxazole-linked [60]fullerene, however, the treatment with methanol for a long time to ensure methanolysis might result in further conversion of the once formed cyano... 

There are two distinct approaches to catenane synthesis the statistical approach, and approaches relying on self-assembly, so-called directed synthesis . The statistical approach relies on the small chance that macrocyclisation may occur while a linear precursor is threaded through a macrocyclic component. Because this is a rather unlikely eventuality, it naturally results in low yields of interlinked product and is chiefly of historical interest. It was this kind of statistical approach that resulted in the first synthesis of a [2] catenane by Wasserman in 1960 (10.64), from cyclisation of the long-chain diester 10.65 while threaded through the annulus of a deuterated C34 cycloalkane 10.66 (Scheme 10.11), 57 Although the overall yield of the catenation reaction was less than 1 %, the existence of the catenane was firmly established. The relatively polar [2] catenane product, along with other polar macrocyclisation reaction products and... 

Wasserman, A. Diels-Alder Reactions Elsevier Publ. Co. Amsterdam, 1965. 

Berdahl, D.R. and Wasserman, H.H. (1983) The reaction of psoralens and related benzofurans with singlet oxygen. An account of current research. Israel Journal of Chemistry, 23 (4), 409—414. 

Alkaloid synthesis from yic-tricarbonyl compounds. Wasserman s group1 has used the strongly electrophilic character of the central carbonyl of a Wc-tricarbonyl system for synthesis of several alkaloids. Thus several isoquinoline alkaloids can be prepared by reaction of a phenethylamine with the tricarbonyl 1. 

Marvell, E. N. in Thermal Electrocyclic Reactions (Wasserman, H. H., ed.) Academic Press, New York 1980... 

Trost, B. M. Sulfuranes in Organic Reactions and Synthesis. 41,1-29 (1973) Tsuji, J. Organic Synthesis by Means of Transition Metal Complexes Some General Patterns. 28, 41-84 (1972) Turley, P. C., see Wasserman, H. H. 47, 73-156 (1974)... 

Another example of LC in this area is the optimizing of photochemical reactions. Dr. H. H. Wasserman and his group at Yale University had a problem similar to that of Dr. Woodward. As shown in Figure 2-21, compound I is converted primarily to compound II in the presence of UV radiation and oxygen. However, concentration and examination of the impurities by LC revealed that compound IV, which was of interest in their research, was present as 0.1% of the reaction mixture. They, therefore, wanted to determine conditions that would increase the yield of compound IV. 

---