131365-11-2

Usage

Uses

Used in Organic Synthesis:
(3-bromoprop-1-yn-1-yl)(tert-butyl)dimethylsilane is used as a reagent in organic synthesis for its ability to facilitate the formation of new chemical bonds and the synthesis of complex organic molecules. Its unique structure allows for selective reactions and the introduction of specific functional groups, making it a valuable tool in the development of pharmaceuticals and other specialty chemicals.
Used in Advanced Material Production:
In the production of advanced materials, (3-bromoprop-1-yn-1-yl)(tert-butyl)dimethylsilane is used as a cross-coupling reagent or a precursor to functionalize silanes and siloxanes. Its incorporation into these materials can enhance their properties, such as thermal stability, mechanical strength, and chemical resistance, which are crucial for applications in aerospace, electronics, and other high-performance industries.
Used in Surface Modification:
(3-bromoprop-1-yn-1-yl)(tert-butyl)dimethylsilane is utilized in the modification of surfaces to create hydrophobic coatings. The introduction of (3-bromoprop-1-yn-1-yl)(tert-butyl)dimethylsilane can alter the surface properties of materials, making them resistant to water, stains, and other environmental factors. This application is particularly relevant in industries such as textiles, automotive, and construction, where durability and maintenance are key considerations.
Used in Specialty Chemicals Manufacturing:
In the manufacture of specialty chemicals, (3-bromoprop-1-yn-1-yl)(tert-butyl)dimethylsilane is employed as a key intermediate or building block. Its unique combination of functional groups allows for the development of novel chemical entities with specific properties tailored to various applications, such as catalysts, sensors, or high-performance polymers.
Overall, (3-bromoprop-1-yn-1-yl)(tert-butyl)dimethylsilane is a multifaceted organosilicon compound with a broad range of applications across different industries, from organic synthesis to the development of advanced materials and surface modification technologies. Its versatility and unique structural features make it an indispensable component in the creation of innovative and high-performance products.

Upstream product

• 120789-51-7 3-tert-butyldimethylsilylpropargyl alcohol 
• 6089-04-9 3-(tetrahydropyran-2'-yloxy)propyne 
• 18162-48-6 tert-butyldimethylsilyl chloride 
• 135294-85-8 tert-butyldimethyl(3-((tetrahydro-2H-pyran-2-yl)oxy)prop-1-yn-1-yl)silane 
• 106-96-7 propargyl bromide 
• 86318-61-8 (tert-butyldimethylsilyl)acetylene 
• 2652-46-2 3-(triethylsilyl)prop-2-yn-1-ol 

Downstream Products

• 848927-39-9 N-(2'-bromoallyl)-N-{3-[tert-butyl(dimethyl)silyl]-2-propynyl}-4-methyl-1-benzenesulfonamide 
• 220913-32-6 DB-67 
• 341519-81-1 2,2-dimethyl-propionic acid 2-[4-(tert-butyl-dimethyl-silanyl)-1-ethynyl-1-hydroxy-but-3-ynyl]-benzyl ester 

Relevant academic research and scientific papers

Palladium-Catalyzed Hydride Addition/C-H Bond Activation Cascade: Cycloisomerization of 1,6-Diynes

The use of ammonium halide salts as metal hydride precursors in a new Pd-catalyzed cycloisomerization of 1,6-diynes, which affords unexplored silylated 2-azafluorenes, is reported. This cascade process includes the addition of a Pd-hydride species to a π-system, intramolecular carbopalladation, and C(sp2)-H bond activation. A variety of functional groups are tolerated, and the synthetic utility of the resulting products has been demonstrated by a series of derivatizations.

The novel silatecan 7-tert-butyldimethylsilyl-10-hydroxycamptothecin displays high lipophilicity, improved human blood stability, and potent anticancer activity

We describe the rational design and synthesis of B- and A,B-ring-modified camptothecins. The key α-hydroxy-δ-lactone pharmacophore in 7-tert-butyldimethylsilyl-10-hydroxycamptothecin (DB-67, 14) displays superior stability in human blood when compared with clinically relevant camptothecin analogues. In human blood 14 displayed a t( 1/2 ) of 130 rain and a percent lactone at equilibrium value of 30%. The tert-butyldimethylsilyl group renders the new agent 25-times more lipophilic than camptothecin, and 14 is readily incorporated, as its active lactone form, into cellular and liposomal bilayers. In addition, the dual 7-alkylsilyl and 10-hydroxy substitution in 14 enhances drug stability in the presence of human serum albumin. Thus, the net lipophilicity and the altered human serum albumin interactions together function to promote the enhanced blood stability. In vitro cytotoxicity assays using multiple different cell lines derived from eight distinct tumor types indicate that 14 is of comparable potency to camptothecin and 10-hydroxycamptothecin, as well as the FDA-approved camptothecin analogues topotecan and CPT-11. In addition, cell-free cleavage assays reveal that 14 is highly active and forms more stable top1 cleavage complexes than camptothecin or SN-38. The impressive blood stability and cytotoxicity profiles for 14 strongly suggest that it is an excellent candidate for additional in vivo pharmacological and efficacy studies.

7-Silylcamptothecins (silatecans): A new family of camptothecin antitumor agents

The synthesis and biological evaluation of about one dozen 7-silylcamptothecin derivatives are described. Most new compounds show potencies comparable to or better than camptothecin itself. The best compound, 11-fluoro-10-amino-7-trimethylsilylcamptothecin, is more than 20 times more potent than camptothecin in cell assays.

Probing o-diphenylphosphanyl benzoate (o-DPPB)-directed C - C bond formation: Total synthesis of dictyostatin

Herein, we report a robust total synthesis of dictyostatin. This polyketide natural product has attracted much attention because of its impressive antiproliferative activity against several human cancer-cell lines. We accomplished its synthesis in a highly convergent manner from three fragments of equal complexity, which were prepared on multigram scale. The southern and northwestern subunits were constructed through application of our o-DPPB-directed hydroformylation and allylic substitution methodology, respectively. These methods generated the C6 and C14 stereocenters of dictyostatin with good diastereoselectivities and simultaneously allowed further elaboration of the fragments by Wittig olefination and Sharpless asymmetric epoxidation, respectively. The compelling performance of the hydroformylation and allylic substitution with regard to practicability, selectivity, and scale underline their value for the construction of propionate motifs.

NEW ARYLALKENYLPROPARGYLAMINE DERIVATIVES EXHIBITING NEUROPROTECTIVE ACTION FOR THE TREATMENT OF NEURODEGENERATIVE DISEASES

The invention relates to novel arylalkenylpropargylamine derivatives of general formula (I) or enantiomers or diastereomers thereof or salts, optionally pharmaceutically acceptable salts, or solvates of any of these. The compounds can be used in treating or preventing a disease or condition in a mammal related to monoamine oxidase dysfunction, especially in neurodegenerative diseases, e.g. Parkinson's disease, Alzheimer's disease or Huntington's disease.

Facile construction of spirocyclopropanated bi-, tri- and tetracyclic skeletons by novel cascades involving intra- and intermolecular heck reactions of 2-bromo-1,6-enynes and bicyclopropylidene

Acyclic 2-bromo-1,6-enynes 5-R, 9-R and 11-R with bulky substituents at the acetylenic terminus were co-cyclized with the highly strained bicyclopropylidene (12) under palladium catalysis at 80 °C to give the cross-conjugated tetraenes 13-R, 18-R and 19-R in moderate-to-good yields (34-71%). Only the co-cyclization of 5-Ph gave rise to an additional product, which was identified as the 11-membered ring 20. At elevated temperatures (120-140 °C) the initially formed tetraenes underwent 6π- electrocyclization to give spiro[cyclopropane-1,4′-bicylo[4.3.0]-1(6),2- dienes] 21-R, 22-R and 23-R. This novel class of spirocyclopropanated oligocycles is also accessible by a one-pot protocol. The highest yields for both the tetraenes and bicyclo[4.3.0]nonadiene and its heteroanalogues were obtained with bulky substituents at the alkyne terminus of the precursors. Heteroatom-containing precursors 9-R and H-R gave lower yields than their all-carbon analogues 5-R. The acyclic 2-bromo-1,8-dien-6-ynes 28a,b,c upon palladium-catalyzed co-cyclization with bicyclopropylidene (12) at 110 °C gave spirocyclopropanated tricycles 31a,b and 32, respectively, in moderate yields (14, 31 and 32%). These products were formed by two consecutive 6π-electrocyclizations. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.

Development of an enantioselective synthetic route to neocarzinostatin chromophore and its use for multiple radioisotopic incorporation

A convergent, enantioselective synthetic route to the natural product neocarzinostatin chromophore (1) is described. Synthesis of the chromophore aglycon (2) was targeted initially. Chemistry previously developed for the synthesis of a neocarzinostatin core model (4) failed in the requisite 1,3-transposition of an allylic silyl ether when applied toward the preparation of 2 with use of the more highly oxygenated substrates 27 and 54. An alternative synthetic plan was therefore developed, based upon a proposed reduction of the epoxy alcohol 58 to form the aglycon 2, a transformation that was achieved in a novel manner, using a combination of the reagents triphenylphosphine, iodine, and imidazole. The successful route to 1 and 2 began with the convergent coupling of the epoxydiyne 15, obtained in 9 steps (43% overall yield) from D-glyceraldehyde acetonide, and the cyclopentenone (+)-14, prepared in one step (75-85% yield) from the prostaglandin intermediate (+)-16, affording the alcohol 22 in 80% yield and with 20:1 diastereoselectivity. The alcohol 22 was then converted into the epoxy alcohol 58 in 17 steps with an average yield of 92% and an overall yield of 22%. Key features of this sequence include the diastereoselective Sharpless asymmetric epoxidation of allylic alcohol 81 (98% yield); intramolecular acetylide addition within the epoxy aldehyde 82, using Masamune's lithium diphenyltetramethyldisilazide base (85% yield); selective esterification of the diol 84 with the naphthoic acid 13 followed by selective cleavage of the chloroacetate protective group in situ to furnish the naphthoic acid ester 85 in 80% yield; and elimination of the tertiary hydroxyl group within intermediate 88 using the Martin sulfurane reagent (79% yield). Reductive transposition of the product epoxy alcohol (58) then formed neocarzinostatin chromophore aglycon (2, 71% yield). Studies directed toward the glycosylation of 2 focused initially on the preparation of the N-methylamino → hydroxyl replacement analogue 3, an α-D-fucose derivative of neocarzinostatin chromophore, formed in 42% yield by a two-step Schmidt glycosylation-deprotection sequence. For the synthesis of 1, an extensive search for a suitable 2′-N- methylfucosamine glycosyl donor led to the discovery that the reaction of 2 with the trichloroacetimidate 108, containing a free N-methylamino group, formed the α-glycoside 114 selectively in the presence of boron trifluoride diethyl etherate. Subsequent deprotection of 114 under mildly acidic conditions then furnished the labile chromophore (1). The synthetic route was readily modified for the preparation of singly and doubly 3H- and 14C -labeled 1, compounds unavailable by other means, for studies of the mechanism of action of neocarzinostatin in vivo.

A direct and stereocontrolled route to conjugated enediynes

A unified synthetic route to 3-hex-en-1,5-diynes, a key building block found in many of the enediyne antitumor agents and designed materials, was developed. The method, which relies on a carbenoid coupling-elimination strategy is tolerant of a wide range of functionalities, and was applied to the synthesis of a variety of linear and cyclic enediynes. Reaction parameters can be adjusted to control stereoselectivity of the process, producing linear enediynes from 1:12 to >100:1 E:Z ratio, and in the case of cyclic enediynes, giving the exclusively Z C-9, C-10, or C-11 products. Key features of the process are the ready availability of precursors and the mildness and efficiency of the reaction. Application of the process in the design of materials precursors and preparation of enediyne antitumor agents are presented.

Stereochemical control in the metallohalocarbenoid route to linear enediynes

Methods for the stereoselective preparation and unmasking of disubstituted Z enediynes are reported. The origins of the unprecedented stereoselectivity of the process are uncovered.

Total synthesis of (-)-dactylynes

The first total synthesis of (-)-dactylyne (1) and (-)-isodactylyne (2), which have been isolated from sea hare, is described in detail. Critical steps in the synthesis include a stereoselective construction as well as an intramolecular ring closure of 32, and the effective double elongation reactions (59 → 63 and 64, 67 → 68, and 70 → 71).