510-70-3

Upstream product

• 10279-82-0 crinan‐3‐one 
• 98301-98-5 (-)-crinan-1-one 
• 41928-89-6 Demethoxy-dihydro-buphanamin 
• 110359-34-7 10-methoxy-crin-2-en-1α-ol 
• 33797-51-2 eschenmoser's salt 
• 51873-62-2 rac-5,12-seco-crinan-12-ol 
• 2635-13-4 1,2-(methylenedioxy)-4-bromobenzene 
• 930-66-5 1-chlorocyclohexene 

Relevant academic research and scientific papers

Total syntheses of (+)- and (?)-Crinane via Pd(0)-Catalyzed deacylative allylation

An efficient Pd(0)-catalyzed deacylative allylation (DaA) of enolcarbonates (pro-nucleophile) prepared from 2-arylcyclohexanones sharing acyl functionality at C2-position with readily available allylic alcohols (pro-electrophiles) by employing Pd(0)-catalysis under mild reaction conditions. The methodology can be extended for deacylative benzylations (DaB) of enolcarbonates of 2-arylcyclohexanones. As an application of our methodology, we have shown asymmetric total synthesis of Amaryllidaceae alkaloids, (+)- and (?)-crinane.

Catalytic deacylative alkylations (DaA) of enolcarbonates: Total synthesis of (±)-Crinane

An efficient Pd(0)-catalyzed deacylative allylation (DaA) of enolcarbonates (as pro-nucleophile) of cycloalkanones sharing acyl functionality at C2-position with readily available allylic alcohols (as pro-electrophiles) is disclosed under mild reaction conditions. A wide variety of cycloalkanones with an aromatic ring and allyl group at C-2 position (all-carbon quaternary center) are obtained in good to excellent yields (36 examples). The usefulness of this methodology has been shown by a total synthesis of Amaryllidaceae alkaloid, (±)-crinane from 2-aryl cyclohexanone in 5 steps.

Diversity-Oriented Approach Toward the Syntheses of Amaryllidaceae Alkaloids via a Common Chiral Synthon

Functionalized hydroindole (1), a common chiral synthon, for versatile transformations to synthesize a broad range of Amaryllidaceae alkaloids (AAs) including (-)-crinine, (-)-crinane, (-)-amabiline, (+)-mesembrine, (-)-maritidine, (-)-oxomaritidine, and

Total Synthesis of (±)-Crinane from 6,6-Dibromobicyclo[3.1.0]hexane Using a 5- exo- trig Radical Cyclization Reaction to Assemble the C3a-Arylated Perhydroindole Substructure

Crinane embodies the tetracyclic framework associated with some of the most common Amaryllidaceae alkaloids. It has now been prepared in 10 steps from 6,6-dibromobicyclo[3.1.0]hexane (2). The initial step involves the thermally induced electrocyclic ring opening of cyclopropane 3 and capture of the resulting π-allyl cation with benzylamine to give an allylic amine that is readily elaborated to the 3°-amine 10. This last compound was engaged in a 5-exo-trig free radical cyclization reaction to give the C3a-arylated perhydroindole 11. Compound 11 was then converted, over two steps, into (±)-crinane, the hydrochloride salt of which has been subjected to single-crystal X-ray analysis.

Concise Total Syntheses of (±)-Joubertiamine, (±)- O -Methyljoubertiamine, (±)-3′-Methoxy-4′- O -methyljoubertiamine, (±)-Mesembrane, and (±)-Crinane

A method to access cis-3a-aryloctahydroindole alkaloids has been developed through a key strategy involving Eschenmoser-Claisen rearrangement of allylalcohol. This approach gives us an opportunity to access the all-carbon quaternary center required for ci

Synthesis of crinane utilizing an allylic sulfoxide for the construction of a hydroindole ring: Via vinylogous C-N bond formation

The synthesis of crinane is disclosed via intramolecular C-N bond formation by the displacement of an allylic sulfoxonium salt. The allylic sulfide precursor was synthesized by a ring-closing metathesis reaction. The quaternary carbon stereocenter was created by alkylation of a benzylic cyanide. The allyl sulfide 14 was prepared by adding vinylmagnesium bromide to an α-chlorosulfide.

Concise total syntheses of (±)-mesembrane and (±)-crinane

A straightforward and unified strategy to access Amaryllidaceae alkaloids comprising a cis-3a-aryloctahydroindole scaffold has been developed. The strategy features Eschenmoser-Claisen rearrangement of allylalcohol as a key step for the installation of al

A general and efficient strategy for 7-aryloctahydroindole and cis-3a-aryloctahydroindole alkaloids: Total syntheses of (±)-γ- lycorane and (±)-crinane

A general and efficient approach to both 7-aryloctahydroindole and cis-3a-aryloctahydroindole alkaloids has been developed. The key step involves Michael additions of the corresponding kinetics and thermodynamics lithium enolates of ketone 9 to the versat

A general efficient strategy for cis-3a-aryloctahydroindole alkaloids via stereocontrolled ZnBr2-catalyzed rearrangement of 2,3-aziridino alcohols

(Matrix presented) A short and general approach to the cis-3a-aryloctahydroindole alkaloids has been developed on the basis of a key stereocontrolled ZnBr2-catalyzed rearrangement of 2,3-aziridino alcohols. Two representative members, (±)-crina

Application of furanyl carbamate cycloadditions toward the synthesis of hexahydroindolinone alkaloids

A convenient synthesis of various substituted hexahydroindolinones has been achieved by an intramolecular Diels-Alder cycloaddition reaction (IMDAF) of furanyl carbamates bearing tethered alkenyl groups. The initially formed [4 + 2]-cycloadduct undergoes nitrogen-assisted ring opening followed by deprotonation of the resulting zwitterion to give the rearranged ketone. The stereochemical outcome of the IMDAF cycloaddition has the sidearm of the tethered alkenyl group oriented syn with respect to the oxygen bridge. A synthetic route to (±)-mesembrane and (±)-crinane was accomplished using this methodology. It was possible to carry out a stereoselective reduction of the initially formed hexahydroindolinone ring to produce the cis-3a-aryl-hydroindole skeleton. A related [4 + 2]-cycloaddition/rearrangement sequence was also used for a formal synthesis of the Chinese ornamental orchid (±)-dendrobine. The tricyclic alkaloid core was formed stereoselectivity from the thermolysis of N-[(2-methyl-2-cyclopentenyl)methyl]-N-(4-isopropyl-furan-2-yl)carbamic acid tert-butyl ester. Kende's advanced intermediate 33 was prepared in seven additional steps by standard transformations, thereby completing a formal synthesis of (±)-dendrobine.