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Volumn 23, Issue 12, 1984, Pages 932-948

The Homoaldol Reaction, or How to Overcome Problems of Regio‐ and Stereo‐selectivity

Author keywords

Homoaldol reaction; Regioselectivity; Stereoselectivity; Synthetic methods

Indexed keywords

LITHIUM COMPOUNDS - CHEMISTRY; ORGANIC COMPOUNDS - SYNTHESIS;

EID: 0021558291     PISSN: 05700833     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.198409321     Document Type: Review
Times cited : (275)

References (288)
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    • The CIP system allows the assignment of the configuration of diastereomers in general formulas only when additional postulates are added [5]. For the purpose of rapid assignment to diastereomeric series we therefore use the syn‐anti prefixes of Masamune et al. [6]. If necessary, they are to be defined through structural formulas.
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    • The term “homoaldol addition” implies that the addition of the starting material leads immediately to homoaldols. Therefore, we name versions that require further deblocking steps as “homoaldol reactions”.
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    • Figure 1 does not take into consideration that the approach of the cation results in a bending of the bond to the C‐1 ligand out of the plane of the allylic system; cf.
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    • The concept of dipole stabilization was introduced by Beak et al. [108, 87]. The term “induced dipole stabilization” refers to the polarization due to the cation [109].
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    • The product ratios are kinetically controlled; we have never obtained any indication of equilibration.
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    • Reetz [121] has in many cases observed an influence of the leaving group in the reagent 150 on the selectivity and postulated the formation of “ate” complexes; cf. also:,. Where tested, we obtained identical results with the chloride 150c and the isopropoxide 150d; only in the case of 150d is the metal exchange slower, which led us to a false interpretation [126]
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    • A case of highly diastereoselective addition to unsymmetrical ketones:lk-addition of (2-alkenyl)triphenoxytitanium derivatives
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    • Results so far obtained allow two hypotheses: titanium compounds of this type are not formed on exchange, or else they react with low selectivity. Z/E‐isomerization is slow (Table 1); cf. also
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    • The reason may be an improved α‐selectivity of the exchange. Moreover, the hydride is commercially available in higher purity than the chloride.
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    • Provided that it does not racemize under the reaction conditions, the (S)‐aldehyde should give the adducts 206 and 207 in enantiomerically pure form.
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    • For a new method for the anti‐selective homoaldol reaction with (E)‐1‐tetrahydropyranyloxy‐2‐butenyl boronates, and for an indirect syn‐selective version; cf.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.