III releases the product and coordinates a second molecule of borane.
It's in the Rhodium archives I think.
II, iII the large substituent of the ketone is aligned inward to avoid steric interactions with the outward-pointing R group of the oxazaborolidine, which is often tethered to the nitrogen atom.
This is the first successful reductive amination in water and in neat conditions.15 (8) Formic acid and formate salts may also be used as reductants in transfer hydrogenations.Edited on by Furch microswitch Harmless Posts: 27 Registered: Member Is Offline Mood: No Mood": Originally posted by Furch To answer the question, by the way, I don't know whether this method has ever been applied to any substance containing the methylenedioxy function.Unless otherwise noted, LibreTexts content is licensed.A one-pot tandem synthetic strategy code promo senseo affords useful secondary amines from benzylic alcohols and anilines via an oxidation-reduction strategy.
Reduction of imines, name Reactions, eschweiler-Clarke Reaction, recent Literature.
Iirc someone applied this method to benzylmagnesium chloride and methylacetimine and succesfully made methamphetamine with a 80 yield.
Initial efforts toward enantioselective ketone reductions focused on the development of chiral, non-racemic reducing agents.
The method allows the efficient synthesis of structurally diverse amines.
Cooperative catalysis of an Ir(III)-diamine complex and a chiral phosphoric acid or its conjugate base enables a direct reductive amination of a wide range of ketones.935 on the topic of "The addition of organometallic compounds to CN bonds "For the addition of an organometallic compound to an imine to give a primary amine, R' in rchnr' would have to be H, and such compounds are seldom stable.(2 transition Metal Catalyzed Reductions edit, transition metal catalyzed reductions may proceed by a variety of mechanisms, depending on the reductant and metal employed.1,2-Dichloroethane (DCE) is the preferred reaction solvent, but reactions can also be carried out in tetrahydrofuran and occasionally in acetonitrile.(4) Chirally modified borohydrides are also useful for enantioselective ketone reductions.Not involve "energetic materials" (i.e.Reductive alkylation of ammonia with aldehydes afforded the corresponding symmetrical secondary amines selectively.An achiral amine in combination with a catalytic amount of a chiral Brønsted acid can accomplish an aldol addition-dehydration-conjugate reduction-reductive amination with 2,6-diketones to provide cyclohexylamines as potential intermediates of pharmaceutically active compounds in good yields and excellent enantioselectivities.Chen, Synthesis, 2017,.Khaksar, Synthesis, 2011, 490-496.Reductions of highly electron-poor CN and CC bonds provide hydrogenation products along with new, stable borylated products.A selective and direct access to secondary amines by reductive mono-N-alkylation of primary amines with carbonyl compounds in the presence of Ti( i -PrO)4 and NaBH4 gave exclusively secondary amines.Tetrahedron: Asymmetry 1995, 6, 31 doi :.1016/0957-4166(94)00344-B.10 Neutral alkoxyboranes may result from these reductions.Also, I don't remember whether the thread concluded that the reaction is versatile or not.
Sugi1, Kiyotaka Yorozu1, Tohru Yamada2 and Teruaki Mukaiyama3 (1) Chemical Synthesis Laboratories, Mitsui Petrochemical Industries, Ltd., Waki-cho, Kuga-gun, Yamaguchi, 740, Japan (2) Department of Chemistry, Faculty of Science and Technology, Keio University, Hiyoshi, Kohoku-ku, Yokohama, 223, Japan (3) Department of Applied Chemistry, Faculty of Science.