A general synthesis of methyl aldulosonates using tris (methylthio) methyl lithium as the ester anion equivalent

Hengeveld, John E.; Grief, Valerie J.; Tadanier, Jack; Lee, C.-M.; Riley, David; Lartey, Paul A.

doi:10.1016/s0040-4039(01)90185-6

Cited by 22 publications

(5 citation statements)

References 7 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The THF was removed by evaporation, and the aqueous layer was extracted several times with dichloromethane/pentane (1:l v/v). The extracts were combined and washed with 10% aqueous sodium bicarbonate, water, and saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, he differences between certain of our results and those reported earlier (2) (ii) From 2,2-bis(methy1thio)-1,3-dithiane A solution of 2,2-bis(methy1thio)-1,3-dithiane (3.24 g, 15.3 mmol) in anhydrous THF (63.3 rnL) was cooled to -78°C under argon. One equivalent of n-butyllithium (1.6 M; 9.56mL) was added, and the mixture was stirred for 1.5 h, allowed to warm to -40°C, added to water, and extracted with carbon tetrachloride.…”

Section: Preparation Of 2-(methy1thio)-l3-dithianecontrasting

confidence: 95%

See 1 more Smart Citation

Reactions of δ-valerolactone with lithio trithio-orthoformates

Yates¹,

Seif-El-Nasr²,

Stanton³

et al. 1991

Can. J. Chem.

View full text Add to dashboard Cite

. 69, 415 (1991) 6-Valerolactone (3), on treatment with tris(methylthio)methyllithium (7) followed by weakly acidic aqueous work-up, gave a tautomeric mixture of 1,1 -bis(methylthio)-6-hydroxy-2-hexanone (80) and tetrahydro-2-bis(methy1thio)methyl-2-pyrao (8b). Under analogous conditions 3 reacted with tris(pheny1thio)methyllithium (10) to form tetrahydro-3-(phenylthiocarbony1)-2-pyranone (11). With 2-(methy1thio)-l,3-dithian-2-yllithium (16) it gave a tautomeric mixture of 2-(5-hydroxy-I-oxopenty1)-2-(methy1thio)-1,3-dithiane (170) (23). The origins of the anomalous products are discussed briefly. It is concluded that because of these anomalies the preparation of tetrahydro-2-hydroxypyran-2-carboxylic acid acetals and related glycosides via trithio-orthoformate derivatives can encounter difficulties, although dithioacetals may serve this purpose.Key words: 1,3-dithianes, a-hydroxy acids, 6-lactones, trithio-orthoformates. (23) i un traitement semblable. On discute brikvement des origines des produits anormaux. Sur la base de ces anomalies, on croit que la preparation des acCtals de l'acide tktrahydro-2-hydroxy-pyran-2-carboxylique et des glycosides apparent&, via les dCrivts trithio-orthoformiates, peut donner lieu i des difficultes, mCme si les dithioacCtals peuvent 6tre utilisks i leur place.

show abstract

Section: Preparation Of 2-(methy1thio)-l3-dithianecontrasting

confidence: 95%

“…Instead it gave a crystalline product, C12H1203S, which is assigned structure 11 (eq. [2] I . L~C(SMC)~ spectrum (6 1.8-2.5 (m, 4H, H-4 and H-5), 3.95 (t, 1 H, H-3), (7) 4.45 (t, 2H, H-6), 7.45 (s,5H,Ph) …”

Section: -(M6thylthio)-l3-dithiane (17b) Le Traitement Du Composc mentioning

confidence: 99%

Reactions of δ-valerolactone with lithio trithio-orthoformates

Yates¹,

Seif-El-Nasr²,

Stanton³

et al. 1991

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…51 (s, 3 H, CH 3 ), 1.97 (dtt, 1 H, 2 J 2¢ax,2¢eq =14.0 Hz, 3 J 2¢ax,1¢ax = 3 J 2¢ax,3¢ax = 12.8 Hz, 3 J 2¢ax,3¢eq =3.1 Hz, 3 J 2¢ax,1¢eq = 3.0 Hz, H-2¢ax), 2.04 (dd, 1 H, 2 J 2a,2b = 14.3 Hz, 3 J 2a,3 = 7.9 Hz, H-2a), 2.13 (dquint, 1 H, 2 J 2¢eq,2¢ax =14.0 Hz, 3 J 2¢eq,1¢ax = 3 J 2¢eq,1¢eq = 3 J 2¢eq,3¢ax = 3 J 2¢eq,3¢eq =2.8 Hz, H-2¢eq), 2.16 (dd, 1 H, 2 J 2b,2a = 14.3 Hz, 3 J 2b,3 = 6.0 Hz, H-2b), 2.60 (dt, 1 H, 2 J 1¢eq,1¢ax =14.0 Hz, 3 J 1¢eq,2¢ax = 3 J 1¢eq,2¢eq = 3.0 Hz, H-1¢eq), 2.66 (dt, 1 H, 2 J 3¢eq,3¢ax =14.0 Hz, 3 J 3¢eq,2¢ax = 3 J 3¢eq,2¢eq = 3.1 Hz, H-3¢eq), 3.00 (ddd, 1 H, 2 J 1ax,1¢eq = 14.0 Hz, 3 J 1¢ax,2¢ax = 12.8 Hz, 3 J 1¢ax,2¢eq =2.6 Hz, H-1¢ax), 3.40 (ddd, 1 H, 2 J 3¢ax,3¢eq = 14.0 Hz, 3 J 3¢ax,2¢ax = 12,8 Hz, 3 J 3¢ax,2¢eq = 2.7 Hz, H-3¢ax), 3.97 (dd, 1 H, 3 J 5,6 =7. 4 Hz,3 J 5,4 =2. 3 Hz, H-5), 4,08 (dd, 1 H, 2 J 7a,7b = 8.6 Hz, 3 J 7a,6 = 5.1 Hz, H-7a), 4.16 (dd, 1 H, 2 J 7b,7a =8.6 Hz, 3 J 7b,6 = 6.2 Hz, H-7b), 4.20 (dd, 3 J 4,3 =5.9 Hz, 3 J 4,5 = 2.…”

Section: Dithioortho Esters 4ab; General Proceduresmentioning

confidence: 98%

“…3 Among them, carbohydratebased chemical synthesis via a two-carbon elongation is the most reliable approach. In particular, very general, short and efficient strategies for the synthesis of various 2ulosonic acids have been developed from the corresponding sugar lactones [4][5][6][7] as exemplified for KDO in Scheme 1.…”

mentioning

confidence: 99%

A New Short and Efficient Route to 3-Deoxy-d-manno-oct-2-ulosonic Acid (KDO) and 3-Deoxy-d-arabino-hept-2-ulosonic Acid (DAH)

Kikelj¹,

Plantier‐Royon²,

Portella³

2006

Synthesis

View full text Add to dashboard Cite

An efficient synthesis of lactones 5 and 6, known intermediates towards KDO and DAH, respectively, has been achieved by a short and highly efficient route. Homologation of protected Dmannose and D-arabinose was performed by a Peterson reaction with 2-lithio-2-trimethylsilyldithiane or the corresponding bis(methylsulfanyl) derivative, followed by the cyclization of the resulting ketene dithioacetal under very smooth conditions. An oxidative treatment with iodine gave the lactones 5 and 6 in a threestep sequence with high yields. Interestingly, this approach can be considered as a general method for the synthesis of various 2-deoxysugar lactones.

show abstract

“…For the required carboxylate anion synthon different tris(alkylthio or arylthio)methyllithiums, derived from tris(alkyl or arylthio)methanes [4], were used successfully in the C 1 elongation of ketones [5] and lactones [6]. Most often [tris(methylthio)methyl]lithium (2) was applied which is stable up to -40ºC [7].…”

Section: Introductionmentioning

confidence: 99%

Unexpected Thorpe Reaction of an α-Alkoxynitrile

Kovács

2000

Molecules

View full text Add to dashboard Cite

α-Alkoxynitrile 1 in the presence of tris(methylthio)methyllithium 2 at -78ºC gave the dimer 5 instead of the expected C 1 -elongated product 3. The formation of compound 5 is explained in terms of anion formation and self-condensation, a variant of the Thorpe reaction. Scrutinizing the 1 H NMR spectra revealed that the enamine tautomer 5b is predominant over the imine 5a in the solvents investigated.

show abstract

A general synthesis of methyl aldulosonates using tris (methylthio) methyl lithium as the ester anion equivalent

Cited by 22 publications

References 7 publications

Reactions of δ-valerolactone with lithio trithio-orthoformates

Reactions of δ-valerolactone with lithio trithio-orthoformates

A New Short and Efficient Route to 3-Deoxy-d-manno-oct-2-ulosonic Acid (KDO) and 3-Deoxy-d-arabino-hept-2-ulosonic Acid (DAH)

Unexpected Thorpe Reaction of an α-Alkoxynitrile

Contact Info

Product

Resources

About