A synthesis of vitamin E in racemic or optically active forms from methacryolein or beta-hydroxyisobutyric acid including intermediates in this synthesis.
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a divisional application of Ser. No. 802,747 filed June 2, 1977--Cohen et al., now U.S. Pat. No. 4,151,205, which in turn is a divisional application of Ser. No. 639,011 filed Dec. 9, 1975--Cohen et al, now U.S. Pat. No. 4,051,153. Said application Ser. No. 639,011 is a continuation-in-part application of U.S. patent application Ser. No. 544,163, Cohen and Saucy, filed Jan. 27, 1975 now U.S. Pat. No. 4,000,161.
This application is also related to U.S. patent application Ser. No. 417,465, filed Nov. 19, 1973, Scott, Parrish and Saucy now U.S. Pat. No. 3,947,473, which is incorporated herein by reference.
A process for asymmetrically hydrogenating through the use of microorganisms a double bond connected to tertiary carbon atom in an olefinic aliphatic compound to produce a tertiary, optically active aliphatic compound useful as an intermediate for optically active Vitamins E and K.
Provided herein is an optically active alcohol having a silyl group, stannyl group, or halogen atom at the .gamma.-position, selected from compounds represented by the general formula [I], ##STR1## the general formula [II], ##STR2## the general formula [III], ##STR3## and the general formula [IV], ##STR4## (where, R denotes a C.sub.1 -C.sub.10 substituted or unsubstituted alkyl group or substituted or unsubstituted phenyl group; A denotes a silyl group represented by ##STR5## a stannyl group represented by ##STR6## or a halogen atom. R.sup.1, R.sup.2, and R.sup.3 are substituted or unsubstituted C.sub.1 -C.sub.10 alkyl groups or substituted or unsubstituted phenyl group, which may be the same or different, provided that this does not apply in the case where A represents a stannyl group or halogen atom in the general formulas [III] and [IV].); a process for producing the same, and a process for resolving the optically active alcohol into isomers of high optical purity.
Novel silyl alcohols having bulky substituents bonded to the silicon, and the silyl group attached to a carbon include the preferred 2-silyl-ethan-1-ols. A method for synthesizing substituted alcohols include hydrosilation of a vinylic ester, especially vinyl acetate, followed by hydrolysis in mild base. The silyl alcohols are useful in preparing phosphorylating reagents for phosphorylating an oligonucleotide. The phosphorylated intermediate bearing the silyl group may be separated from failure product on the basis of bulky substituents on the silyl protecting group, which is later removed, e.g. by fluoride ion.
Processes for synthesizing tertiary alkynols by reacting carbonyl-group-containing compounds with alkynes in the presence of a basic catalyst are disclosed. Preferred products are 6,10,14-trimethyl-4-pentadecyn-6-ol compounds having the structure: ##STR1## A preferred, novel compound, 6,10,14-trimethyl-4-pentadecyne-2,6-diol, can be used in the synthesis of Vitamin E or Vitamin K.sub.1.
