Cyclohexenylboration of Aldehydes and Ketones with the Borabicyclo[3.3.2]decanes (BBDs)

Eduvigis González, Lorell Muñoz-Hernández, Eyleen Alicea, Bakthan Singaram, George Kabalka, John A. Soderquist

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Asymmetric hydroboration of 1,3-cyclohexadiene with 4R produces the allylborane 5RR as essentially a single diastereomer (i.e., no observable 5RS), and its addition to representative aldehydes provides 9RS (52-75%) with excellent selectivity (94-99% ee). By contrast, a similar sequence with the 10-Ph-BBD reagent, 14R, results in a ca. 45:55 mixture of 15RR and 15RS. However, their addition to methyl ketones provides the corresponding 3°-homoallylic alcohols (18RS) with excellent selectivity (80-99% ee) but in low yields (15-52%) because 15RS is unreactive toward either allylboration or isomerization to 15RR. Thus, with 2 equiv of 15, the yield of 18 (R = Ph) is increased from 52% to 85%. Boranes 5SS and 15SS provide enantiomeric alcohols.

Original languageEnglish (US)
Pages (from-to)4368-4371
Number of pages4
JournalOrganic letters
Volume17
Issue number17
DOIs
StatePublished - Aug 18 2015

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Ketones
aldehydes
Aldehydes
ketones
alcohols
selectivity
Alcohols
hydroboration
Boranes
boranes
Isomerization
isomerization
reagents
decane
1,3-cyclohexadiene

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

González, E., Muñoz-Hernández, L., Alicea, E., Singaram, B., Kabalka, G., & Soderquist, J. A. (2015). Cyclohexenylboration of Aldehydes and Ketones with the Borabicyclo[3.3.2]decanes (BBDs). Organic letters, 17(17), 4368-4371. https://doi.org/10.1021/acs.orglett.5b02194

Cyclohexenylboration of Aldehydes and Ketones with the Borabicyclo[3.3.2]decanes (BBDs). / González, Eduvigis; Muñoz-Hernández, Lorell; Alicea, Eyleen; Singaram, Bakthan; Kabalka, George; Soderquist, John A.

In: Organic letters, Vol. 17, No. 17, 18.08.2015, p. 4368-4371.

Research output: Contribution to journalArticle

González, E, Muñoz-Hernández, L, Alicea, E, Singaram, B, Kabalka, G & Soderquist, JA 2015, 'Cyclohexenylboration of Aldehydes and Ketones with the Borabicyclo[3.3.2]decanes (BBDs)', Organic letters, vol. 17, no. 17, pp. 4368-4371. https://doi.org/10.1021/acs.orglett.5b02194
González E, Muñoz-Hernández L, Alicea E, Singaram B, Kabalka G, Soderquist JA. Cyclohexenylboration of Aldehydes and Ketones with the Borabicyclo[3.3.2]decanes (BBDs). Organic letters. 2015 Aug 18;17(17):4368-4371. https://doi.org/10.1021/acs.orglett.5b02194
González, Eduvigis ; Muñoz-Hernández, Lorell ; Alicea, Eyleen ; Singaram, Bakthan ; Kabalka, George ; Soderquist, John A. / Cyclohexenylboration of Aldehydes and Ketones with the Borabicyclo[3.3.2]decanes (BBDs). In: Organic letters. 2015 ; Vol. 17, No. 17. pp. 4368-4371.
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abstract = "Asymmetric hydroboration of 1,3-cyclohexadiene with 4R produces the allylborane 5RR as essentially a single diastereomer (i.e., no observable 5RS), and its addition to representative aldehydes provides 9RS (52-75{\%}) with excellent selectivity (94-99{\%} ee). By contrast, a similar sequence with the 10-Ph-BBD reagent, 14R, results in a ca. 45:55 mixture of 15RR and 15RS. However, their addition to methyl ketones provides the corresponding 3°-homoallylic alcohols (18RS) with excellent selectivity (80-99{\%} ee) but in low yields (15-52{\%}) because 15RS is unreactive toward either allylboration or isomerization to 15RR. Thus, with 2 equiv of 15, the yield of 18 (R = Ph) is increased from 52{\%} to 85{\%}. Boranes 5SS and 15SS provide enantiomeric alcohols.",
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