The enantioselective synthesis of spirocycles has been a long time pursued dream for organic chemists. Since the first pioneering efforts of Tamao and coworkers in the enantioselective construction of spirosilanes, many efforts have been devoted to the development of new and promising asymmetric methodologies. Remarkably, with the advent of organocatalysis the number of methodologies has been highly increased. The aim of this tutorial review is to summarize the last trends and developments reported in the literature in the enantioselective synthesis of spirocompounds.

Enantioselective methodologies for the synthesis of spiro compounds

Regioselective cross-coupling reactions of multiple halogenated nitrogen-, oxygen-, and sulfur-containing heterocycles

Spirocycles provide an exciting platform to develop and understand the reactivity and selectivity for a wide variety of catalysts while affording diverse strategies to access molecules with importa...

Asymmetric Catalysis for the Synthesis of Spirocyclic Compounds

Chiral compounds occupy a large and important area of organic molecules, such as natural products, bioactive compounds, drugs, and functional materials. However, examples of the synthesis of chiral organosilicon compounds are still rare among organic compounds. It is important to construct a quaternary silicon atom to synthesize chiral organosilicon compounds. Our strategy for the construction of a quaternary silicon atom is a rhodium-catalyzed double dehydrogenative cyclization of bis(biphenyl)silanes through carbon–silicon bond formation (Scheme 1). 3] We report herein the asymmetric synthesis of chiral spirosilabifluorene derivatives from bis(biphenyl)silanes, bearing substituents on the aromatic rings, using a rhodium catalyst with a chiral phosphine ligand.

Rhodium-catalyzed asymmetric synthesis of spirosilabifluorene derivatives

This review describes important recent advancements in asymmetric cycloisomerization reactions. A wide variety of catalytic and asymmetric strategies have been applied to these reactions over the past twenty years. Cycloisomerization reactions have the ability to produce diverse polycyclic compounds in excellent yields and selectivity. They constitute a powerful and efficient strategy for asymmetric carbon-carbon bond formation in cyclic compounds. Enyne and related olefin cyclizations comprise the majority of reactions of this type and important advances have recently occurred in this area. However, significant changes have also occurred in the area of classical cyclization as well as intramolecular hydroacylation and C–H activation initiated cyclization and these will also be described.

/pdf/catalytic-enantioselective-carbon-carbon-bond-formation-34ph8ykkns.pdf

Catalytic enantioselective carbon-carbon bond formation using cycloisomerization reactions

Axially Chiral Spirosilanes via Catalytic Asymmetric Intramolecular Hydrosilation

Asymmetric Reduction of Ketones with Microbes (Commemoration Issue Dedicated to Professor Shinzaburo OKA On the Occasion of His Retirement) Author(s) Nakamura, Kaoru; Kawai, Yasushi; Kitayama, Takashi; Miyai, Takehiko; Ogawa, Masahiko; Mikata, Yuji; Higaki, Masato; Ohno, Atsuyosi Citation Bulletin of the Institute for Chemical Research, Kyoto University (1989), 67(3): 157-168 Issue Date 1989-11-30

Asymmetric Reduction of Ketones with Microbes

A series of 2,3-bis(siloxy)-1,4-bis(diphenylphosphino)butanes SILOPs, possessing various siloxy groups, and their Rh(I) complexes have been prepared. The X-ray structure of a SILOP shows a staggered conformation with two siloxy groups in the anti positions. The X-ray crystal structure of a cationic Rh(I)-SILOP complex, however, shows an anti arrangement of not the two siloxy groups but the two silyl groups with respect to the O–O axis, which reinforces the C2-symmetrical environment around the metal center.

K. Nakamura

Papers

Axially Chiral Spirosilanes via Catalytic Asymmetric Intramolecular Hydrosilation

Asymmetric Reduction of Ketones with Microbes

New Chiral Diphosphines, 2, 3-Bis(Siloxy)-1, 4-bis(diphenylphosphino)butanes, and Their Cationic Rh(I) Complexes : Synthesis and Structures

Stereochemical Control in Microbial Reduction. Part 19. Effect of Heat- Treatment on the Diastereoselectivity in the Reduction with Bakers′ Yeast.

A New, Highly Efficient, and Simple Procedure for the Construction of Medium-Sized Nitrogen Heterocyclic Ring System.