Construction of Spiro Skeletons in 2,2',3,3'-Tetrahydro-1,1'- spirobi[1H-indene]-7,7'-diol (SPINOL) and Analogues

doi:10.6023/cjoc202103053

Abstract

1,1'-Spirobiindane possesses a new type of skeleton for chiral ligands developed in the early 21st century, which has the characteristics of C₂-symmetry, strong rigidity, high stability, and ease of modification. Zhou et al. developed 2,2',3,3'-tetrahydro-1,1'-spirobi[1H-indene]-7,7'-diol (SPINOL) into series of chiral ligands and catalysts, and achieved great success in the field of catalytic asymmetric synthesis. These ligands and catalysts bearing 1,1'-spirobiindane skeleton are considered as few “privileged chiral ligands and catalysts”. Though catalytic asymmetric syntheses have appeared, in the present methods SPINOL and analogues are usually obtained in racemic forms, which require further chiral resolution. Laborious synthetic and resolution steps limit their productions in industrial scale. Therefore, it is urgent as well as challenging to develop efficient method of asymmetric catalytic synthesis of chiral spiro ligands from cheap and readily available raw materials. The synthetic methods of SPINOL and analgoues in the past 20 years are summarized, including those bearing heteroatoms in the spiro skeleton, in the hope of sparking new ideas for the construction of spiro skeletons in ligands or catalysts.

Key words: 2,2',3,3'-tetrahydro-1,1'-spirobi[1H-indene]-7,7'-diol (SPINOL), construction of spiro skeleton, C₂-symmetric ligand, chiral resolution

Cite this article

Qihang Zhao, Longchang Tang, Peng Jiao. Construction of Spiro Skeletons in 2,2',3,3'-Tetrahydro-1,1'- spirobi[1H-indene]-7,7'-diol (SPINOL) and Analogues[J]. Chinese Journal of Organic Chemistry, 2021, 41(9): 3400-3413.

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Fig. & Tab. 21

Figure 1. Comparison of spiro[4.4]nonane-1,6-diol/dione with SPINOL

Figure 2. Valuable SPINOL derivatives

Figure 3. SPINOL analogues

Scheme 1. SPINOL synthesis and separation by Birman

Figure 4. Split reagents that proved to be unavailable for SPINOL

Scheme 2. Synthesis and resolution of CHEXDBSPINOL

Scheme 3. Synthesis of 2,2'-substituted SPINOL derivative 11

Scheme 4. Enantioselective synthesis of CHEXDBSPINOL

Scheme 5. Enantioselective synthesis of 3,3'-substituted SPINOL derivative 17

Scheme 6. Synthesis of SPINOL analogues from bisphenol C or bisphenol A

Scheme 7. Reaction mechanism of the formation of 23 from bisphenol A

Figure 5. Spiro skeletons bearing heteroatoms

Scheme 8. Synthesis and application of a chiral ligand based on O-SPINOL

Scheme 9. Synthesis of bisphosphine ligand SPANphos bearing spirobichroman skeleton

Scheme 10. Construction of spirobischroman skeleton

Scheme 11. Synthesis of bisphosphine ligand SKP bearing spirobichroman skeleton

Scheme 12. Asymmetric synthesis of compounds bearing spiro ketal skeleton

R^a	Ligand^b	Yield/%	ee/%
MOM	L5	97	94
Bn	L5	82	91
MOM	L6	97	99
Bn	L6	99	98
BOM	L6	91	99

Table 1. Asymmetric synthesis of starting chiral benzyl alcohols for SPIROL 36

Scheme 13. Synthesis and resolution of SBIDOL

Scheme 14. Synthesis and resolution of aza-SPINOL analogue

Scheme 15. Catalytic asymmetric synthesis of silicon-centered SPINOL analogue

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1,1'-螺二氢茚-7,7'-二酚(SPINOL)及类似物中螺环骨架的构建方法