Chlorodiphenylsilane1

[1631-83-0]  · C12H11ClSi  · Chlorodiphenylsilane  · (MW 218.76)

(hydrosilylation;1 precursor to alkyldiphenyl- and aryldiphenylsilanes2)

Physical Data: bp 140-145 °C/7 mmHg (99-101 °C/1 mmHg; 83-85 °C/0.4 mmHg); d 1.137 g cm-3; n 1.5845.

Solubility: sol benzene, chloroform, carbon tetrachloride, and ether.

Form Supplied in: liquid. Commercially available.

Preparative Methods: chlorodiphenylsilane may be prepared in high yield by treatment of diphenylsilane with triphenylmethyl chloride in refluxing benzene3 or with PCl5 at rt in CCl4.4

Handling, Storage, and Precautions: moisture sensitive. Reactions are typically conducted under an inert atmosphere. The compound is corrosive and liberates HCl upon contact with moisture; may burn exposed skin and can be destructive to eyes, mucous membranes, and upper respiratory tract. Chemically incompatible with water, alcohols, and amines.

Hydrosilylation of Alkenes and Alkynes.

In the presence of a catalyst (typically chloroplatinic acid, H2PtCl2), chlorodiphenylsilane hydrosilylates double and triple bonds. As a difunctional reagent, chlorodiphenylsilane may be used in a reaction with an organometallic reagent (see the following section) to displace chlorine prior to the hydrosilylation reaction as in eq 15 or hydrosilylation may be conducted first with subsequent reaction at silicon as illustrated in eq 2.6 The regiochemistry of the reaction has been reviewed.7

An enantioselective synthesis of chiral diols via intramolecular hydrosilylation using a chiral catalyst followed by oxidative cleavage of the Si-C bond (with retention of configuration) has been reported.8 Intramolecular hydrosilylation/oxidation of allylamines provides a highly regio- and stereoselective synthesis of 2-amino alcohols (eq 3).9

Chloride Displacement by Organometallic Reagents.

Organolithium and Grignard reagents react with chlorodiphenylsilane to produce substituted alkyl- or aryldiphenylsilanes (eqs 4 and 5).2

Related Reagents.

Triethylsilane.


1. (a) Jones, D. N. In Comprehensive Organic Chemistry; Barton, D. H. R., Ed.; Pergamon: New York, 1979; Vol. 3, pp 567-571. (b) Chalk, A. J. Trans. N. Y. Acad. Sci. 1970, 32, 481.
2. (a) Buynak, J. D.; Strickland, J. B.; Lamb, G. W.; Khasnis, D.; Modi, S.; Williams, D.; Zhang, H. JOC 1991, 56, 7076. (b) Tacke, R.; Strecker, M.; Sheldrick, W. S.; Heeg, E.; Berndt, B.; Knapstein, K. M. CB 1980, 113, 1962.
3. Cory, J. Y.; West, R. JACS 1963, 85, 2430.
4. Mawaziny, S. JCS(A) 1970, 1641.
5. Merkl, G.; Berr, K. P. TL 1992, 33, 1601.
6. Brook, A.; Kucera, H. W. JOM 1975, 87, 263.
7. E. W. Colvin, Silicon in Organic Synthesis; Butterworths: Boston, 1981; pp 46-48, 325-331.
8. Bergens, S. H.; Noheda, P.; Whelan, J.; Bosnich, B. JACS 1992, 114, 2121.
9. Tamao, K.; Kakagawa, Y.; Ito, Y. JOC 1990, 55, 3438.

Dallas K. Bates

Michigan Technological University, Houghton, MI, USA



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