81790-10-5 Usage
Physical properties
bp 46–50°C/20 mmHg,64–65°C/38–
39 mmHg.
Uses
2-Bromo-3-trimethylsilyl-1-propene can be used as synthon for CH2=C?CH2TMS1–3 and CH2=CBrC?H2;2 for
synthesis of 1-trimethylsilylmethyl-substituted 1,3-butadienes.The 1-trimethylsilylmethylvinyl
anion CH2=C(M)CH2TMS (2) (M = Li, Mg, Cu,
etc.), readily prepared from 2-bromo-3-trimethylsilyl-1-propene
(1) under typical conditions, allows the introduction of the
synthetically useful 1-trimethylsilylmethylvinyl group to a wide
variety of substrates. Ring opening of 1-butene oxide with the
Grignard reagent (2) (M = MgBr) in the presence of copper(I)
iodide gives only one regioisomer. Subsequent desilylative oxidation
of this allyl alcohol to α-methylene-γ-lactones provides
further utility of (1) as a 1-hydroxymethylvinyl anion equivalent,
i.e. CH2=?C?CH2OH (eq 1).Alternatively, the alcohol
from trans-2,3-epoxybutane provides a route to the unstable sixmembered
β,γ-unsaturated lactone (eq 2).The copper-catalyzed
1,4-addition to the typically unreactive mesityl oxide proceeds
smoothly. The versatility of the allylsilane moiety is again illustrated
in the ethylaluminum dichloride-induced cyclization of the
adduct to a tertiary cyclopentanol in high yield (eq 3).
Preparation
reaction of 2,3-dibromopropene
with lithium (trimethylsilyl)cuprate in HMPA at 0°C
(63–90%);(2) reaction of 2,3-dibromopropene with trichlorosilane
in the presence of trichlorosilane and copper(
I) chloride, followed by treatment with methylmagnesium
bromide (63–71%).
Purification Methods
It is fractionally distilled through an efficient column. It is flammable. [Trost & Chan J Am Chem Soc 104 3733 1982, Trost & Coppola J Am Chem Soc 104 6879 1982.]
Check Digit Verification of cas no
The CAS Registry Mumber 81790-10-5 includes 8 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 5 digits, 8,1,7,9 and 0 respectively; the second part has 2 digits, 1 and 0 respectively.
Calculate Digit Verification of CAS Registry Number 81790-10:
(7*8)+(6*1)+(5*7)+(4*9)+(3*0)+(2*1)+(1*0)=135
135 % 10 = 5
So 81790-10-5 is a valid CAS Registry Number.
InChI:InChI=1/C6H13BrSi/c1-6(7)5-8(2,3)4/h1,5H2,2-4H3
81790-10-5Relevant articles and documents
SilverCatalyzed Cascade Carboxylation and Cyclization of Trimethyl(2-methylenebut-3-yn-1-yl)silane Derivatives
Sekine, Kohei,Sadamitsu, Yuta,Yamada, Tohru
supporting information, p. 5706 - 5709 (2015/12/01)
C-C bond-forming carboxylation and cyclization of trimethyl(2-methylenebut-3-yn-1-yl)silane derivatives and carbon dioxide was developed. Silver catalysts and CsF promoted the reaction to afford the corresponding 2-furanone and 2-pyrone derivatives in goo
Synthesis of 2,6-cis-disubstituted 4-methylenetetrahydropyrans by oxy-Michael addition
Gill, Duncan,Taylor, Nicholas H.,Thomas, Eric J.
scheme or table, p. 5034 - 5045 (2011/08/06)
The combination of an 'ene' reaction between a 2-(2-trialkylsilyloxyalkyl) prop-2-enyl(trimethyl)silane and an alk-1-yn-3-one mediated by zinc(II) iodide, and an intramolecular oxy-Michael reaction, provides an efficient synthesis of cis-2,6-disubstituted 4-methylenetetrahydropyrans of interest in the context of a synthesis of bryostatins. The stereoselective formation of (E)-vinylsilanes in the 'ene' reaction is of interest.
Versatile synthesis of bicyclo[9.3.1]pentadecatriene for new bicyclic taxoids
Shibuya, Satoshi,Isobe, Minoru
, p. 373 - 374 (2007/10/03)
A common carbon skeleton bicyclo[9.3.1]pentadecatriene of taxachitrienes was synthesized in its des-methyl form in short steps. The key step was Nicholas-Hosomi type reaction in the acidic cyclization between ene-yne biscobalthexacarbonyl complex electrophile with allyltrimethylsilane nucleophile. Decomplexation of the biscobalthexacarbonyl was achieved with a tin hydride and NBS in 1,4-cyclohexadiene solvent.
