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Methyl vinyl ketone

About: Methyl vinyl ketone is a research topic. Over the lifetime, 1510 publications have been published within this topic receiving 26839 citations. The topic is also known as: 3-buten-2-one & gamma-oxo-alpha-butylene.


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Journal ArticleDOI
TL;DR: In this paper, a reaction sequence of trimethyl-hydroquinone with methyl vinyl ketone in acidic methanol gave rac.-2methoxy-2,5,7,8,8-tetramethyl-chroman-6-ol (8), which was converted to (2R, 4′R, 8′R)-α-tocopherol (1d) using a side chain derived from phytol.
Abstract: Reaction of trimethyl-hydroquinone with methyl vinyl ketone in acidic methanol gave rac.-2-methoxy-2,5,7,8-tetramethyl-chroman-6-ol (8). This acetal was converted in four steps to rac.-(6-hydroxy-2,5,7,8-tetramethyl-chroman-2-yl)acetic acid (13). Acid 13 was readily resolved with α-methyl-benzylamine to give the (S)-enantiomer 14. Treatment of the unwanted (2 R)-isomer with acid regenerated 13, thus leading to an efficient use of this compound. Employing a side chain derived from phytol, 14 was converted to (2R, 4′R, 8′R)-α-tocopherol (1d, ‘natural’ vitamin E). A reaction sequence from 14 involving two highly stereoselective Claisen rearrangements has provided the first total synthesis of (2R,'E,7′E)-α-tocotrienol (2d).

75 citations

Journal ArticleDOI
TL;DR: The five-coordinate complex OsHCl(CO)(PiPr3)2 (1) reacts with KOH in methanol to give the hydroxo derivative OsH(OH)(CO) (2) as mentioned in this paper.

74 citations

Journal ArticleDOI
TL;DR: In this paper, a series of chiral bifunctional thiourea-phosphane catalysts were synthesized and successfully applied in the catalytic, asymmetric allylic amination of MBH (Morita-Baylis-Hillman) acetates derived from the methyl vinyl ketone (MVK), with phthalimide, affording the amination products in up to over 99 % yield and 90 % ee.

73 citations

Journal ArticleDOI
TL;DR: The collective studies suggest that intramolecular hydrogen bonding plays a key role in both activating the alpha-aminoaldehyde toward addition and directing facial selectivity.
Abstract: Rhodium-catalyzed hydrogenation of methyl vinyl ketone and ethyl vinyl ketone in the presence of N-Boc-alpha-aminoaldehydes 3a-8a at ambient temperature and pressure results in reductive C-C coupling to furnish aldol adducts 3b-8b and 3c-8c, respectively, which incorporate stereotriads that embody high levels of syn-aldol selectivity accompanied by high levels of anti-Felkin-Anh control. The collective data are consistent with a catalytic mechanism involving addition of the Z(O)-rhodium enolate to the sterically less-encumbered aldehyde pi-face of an intramolecularly hydrogen-bonded chelate through a Zimmerman-Traxler type transition structure. Stereochemical assignments are supported by single-crystal X-ray diffraction analysis of 5b-O-3,5-dinitrobenzoate, iso-5b, N-Me-iso-5b-O-3,5-dinitrobenzoate, and 7b. As revealed by HPLC analysis, optical purity of the stereochemically labile alpha-aminoaldehydes is completely preserved under the conditions of hydrogen-mediated aldol coupling. Deletion of the intramolecular hydrogen bond, as in the case of N-methyl-N-Boc-l-leucinal N-Me-5a, inverts stereoselectivity to furnish the Felkin-Anh product N-Me-iso-5b in 17% yield. Additionally, reactions performed in the presence of tert-amyl alcohol (10 equiv) exhibit markedly lower levels of anti-Felkin-Anh control (7:1 versus > or = 20:1). The collective studies suggest that intramolecular hydrogen bonding plays a key role in both activating the alpha-aminoaldehyde toward addition and directing facial selectivity.

71 citations


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Performance
Metrics
No. of papers in the topic in previous years
YearPapers
20238
202249
202121
202020
201910
201817