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1,3-Bis[tris(hydroxymethyl)methylamino]propane is used as a buffer for polymerase chain reaction and molecular biology. It is also used with hydrochloric acid buffer for stabilization of farnesyl diphosphate isolated from a strain of saccharomyces cerevisiae. It acts as a ligand and forms dinuclear hydroxo complexes with Lanthanides(III). Further, it is useful for calibration of genetically encoded pH indicators expressed in the cytosol or mitochondria. It is also employed to investigate the influence of anions with varying nucleophilic properties on the autoxidation of oxymyoglobin. In addition to this, it is used in the purification of glucose-binding protein from membranes of sulfolobus solfataricus and as a non-zwitterionic buffer, which is used in the pH range between 6.3 and 9.5.
The 2-lithio derivative, normally generated with n-BuLi, behaves as a formyl anion equivalent. It has been shown that the rigorous exclusion of atmospheric oxygen minimizes side reactions and is critical in obtaining optimum results in these lithiation procedures: J. Org. Chem., 60, 4258 (1995).
Monoalkylation of the 2-lithio-derivative and cleavage of the dithiane leads to an aldehyde. Successive dialkylation provides a route to ketones. For reviews of the reversal of the normal reactivity of groups, "umpolung", see: Angew. Chem. Int. Ed., 18, 239 (1979), and of the umpolung of carbonyl activity through sulfur-containing reagents: Synthesis, 357 (1977). See also 1,3-Propanedithiol, A15261, 1,3-Dithiolane, L11914, and 1,2-Ethanedithiol, L12865.
For an example of successive acylation and alkylation of 1,3-dithiane, which can be carried out as a one-pot sequence, see: Synthesis, 625 (1980).
Reaction with 2-cyclohexenone proceeds via 1,2-addition. For details of this and subsequent cleavage and rearrangement, see: Org. Synth. Coll., 8, 309 (1993):
Cleavage of 1,3-dithianes has been effected by a variety of methods, including:
Chloramine-T: Synth. Commun., 2, 7 (1972); NCS, AgNO3, acetonitrile-water: J. Org. Chem., 36, 3553 (1971); 48, 1552 (1983); SO2Cl2, silica, DCM-water: Synthesis, 678 (1976); Bromodimethylsulfonium bromide (from DMSO and bromine): Synthesis, 720 (1979); DMSO-HCl-dioxane: Synthesis, 679 (1982); CuCl2, CuO, acetone: Org. Synth. Coll., 6, 109 (1988); CAN, acetonitrile-water: Synth. Commun., 11, 423 (1981); DDQ, acetonitrile-water: J. Chem. Soc., Perkin 1, 453 (1996); Phenyl phosphorodichloridate, NaI, acetonitrile-DMF: Tetrahedron Lett., 29, 5471 (1988); Glyoxylic acid in AcOH: Synthesis, 694 (1976); HIO4, THF-ether: Tetrahedron Lett., 37, 4331 (1996); PhI(OAc)2, acetone-water: Syn. Commun., 30, 4081 (2000). For facilitation of cleavage of 1,3-dithianes by S-alkylation, see Trimethyloxonium tetrafluoroborate, A15175.
For conversion to the dithienium salt by hydride abstraction, see Triphenylcarbenium tetrafluoroborate, A12949.
Reviews: Synthetic uses of 1,3-dithianes: Tetrahedron, 45, 7643 (1989); Chemistry of 1,3-dithioacetals: Organosulfur Chemistry, P. Page, Ed., Academic Press N.Y. (1995).
Li, H.; Shao, B.; Li, Y.; Chen, L.; Zhao, J. Two octamolybdate-based hybrids functionalized by 1,3-bis[tris(hydroxymethyl)methylamino]propane ligand. Inorg. Chem. Commun. 2015, 61, 68-72.
Ludeman, J. P.; Nazari-Robati, M.; Wilkinson, B. L.; Huang, C.; Payne, R. J.; Stone, M. J. Phosphate modulates receptor sulfotyrosine recognition by the chemokine monocyte chemoattractant protein-1 (MCP-1/CCL2). Org. Biomol. Chem. 2015, 13 (7), 2162-2169.